Pyrrole derivatives useful as diazo and coupling components

ABSTRACT

Pyrrole derivatives of the formula ##STR1## or the tautomers thereof, where R 1  is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, hetaryl or amino, it being possible for these radicals to be substituted, 
     R 2  is hydrogen, alkyl, benzyl, alkenyl, cycloalkyl or phenyl 
     R 3  is hydrogen, alkyl, benzyl or alkenyl, or R 2  and R 3  together are ##STR2##  where T 1 , T 2  and T 3  have the meanings mentioned in the description, or R 2  and R 3  together with the nitrogen connecting them are a heterocyclic radical, 
     R 4  is cyano, or carbamoyl or thiocarbamoyl, each of which can be substituted, or --C(NH 2 )═N--OH, 
     R 5  is halogen, hydroxyl, alkanoyloxy or benzoyloxy and 
     R 6  is hydrogen, alkyl, phenyl, cyano, halogen, nitro, hydroxysulfonyl, alkanoyl, benzoyl or ##STR3##  where T 4  is alkyl or phenyl and T 5  is the radical of an active methylene compound, hydroxyimino or the radical of a primary amine, 
     with the proviso that R 1 , R 2  and R 3  are not all hydrogen, a process for the preparation of pyrrole derivatives (with R 5  =hydroxyl) and the use of the novel products as diazo or coupling components are described.

The present invention relates to compounds of the general formula I ##STR4## or the tautomers thereof, where

R¹ is hydrogen, C₁ -C₂₀ -alkyl which can be substituted and/or interrupted by one or more oxygens, C₃ -C₆ -alkenyl which can be substituted, C₃ -C₆ -alkynyl which can be substituted, C₃ -C₁₀ -cycloalkyl which can be substituted, phenyl which can be substituted, pyridyl, thienyl, amino, C₁ -C₄ -alkanoylamino, benzoylamino, C₁ -C₄ -dialkylamino or ##STR5## where X¹ is C₁ -C₄ -alkyl or phenyl, and X² is C₁ -C₄ -alkyl, alkyl,

R² is hydrogen, C₁ -C₄ -alkyl, benzyl, C₃ 14 C₆ -alkenyl, C₅ -C₇ -cycloalkyl, or phenyl which can be substituted,

R³ is hydrogen, C₁ -C₄ -alkyl, benzyl or C₃ -C₆ -alkenyl, or R² and R³ together are ##STR6## where T¹ is hydrogen, C₁ -C₄ -alkyl or phenyl, T² is C¹ -C₄ -alkyl, or phenyl which can be substituted, and T³ is C₁ -C₄ -alkyl, or R² and R³ together with the nitrogen connecting them are a 5- to 7-membered saturated heterocyclic radical which can contain other hetero atoms.

R⁴ is cyano, carbamoyl, C₁ -C₄ -mono- or dialkylcarbamoyl, thiocarbamoyl, C₁ -C₄ -mono- or dialkylthiocarbamoyl or ##STR7##

R⁵ is halogen, hydroxyl, C₁ -C₂₀ -alkanoyloxy, or benzoyloxy which can be substituted, and

R⁶ is hydrogen, C₁ -C₄ -alkyl, phenyl which can be substituted, cyano, halogen, nitro, hydroxysulfonyl, C₁ -C₁₀ -alkanoyl, benzoyl which can be substituted, or ##STR8## where T⁴ is C₁ -C₄ -alkyl, or phenyl which can be substituted, and T⁵ is the radical of an active methylene compound, hydroxyimino or N--X³ where X³ is C₁ -C₂₀ -alkyl which can be substituted and/or interrupted by one or more oxygens, C₃ -C₆ -alkenyl which can be substituted, C₃ -C₆ -alkynyl which can be substituted, C₃ -C₁₀ -cycloalkyl which can be substituted, phenyl which can be substituted, pyridyl, C₁ -C₄ -alkoxycarbonylmethyl, amino, C₁ -C₄ -dialkylamino or phenylamino, with the proviso that R¹, R² and R³ are not all hydrogen.

DD-A-126,389 discloses 5-methyl- and 5-ethyl-2-amino-3-cyanopyrrolin-4-one. However, these compounds are not particularly suitable as diazo components for the preparation of azo dyes.

The object of the present invention was to prepare novel pyrrole derivatives which are suitable, depending on the constitution, both as diazo components and as coupling components.

In accordance with this, we have found the pyrrole derivatives of the formula I which are identified in the introduction.

All the alkyls and alkenyls occurring in the abovementioned formula I can be both straight-chain and branched.

When alkyls which are interrupted by one or more oxygens occur in the formula I, the preferred alkyls are interrupted by one to three, in particular one or two, oxygens.

When substituted phenyls occur in the formula I, examples of suitable substituents are C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, especially chlorine or bromine, nitro, hydroxyl or amino.

When substituted alkyls occur in the formula I,

examples of suitable substituents are C₁ -C₅ -alkylthio, phenoxy which can be substituted, halogen, especially chlorine or bromine, hydroxyl, amino, C₁ -C₄ -mono- or dialkylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C₁ -C₄ -alkyl)piperazino, hexamethyleneimino, C₁ -C₅ -alkoxycarbonyl, or phenyl which can be substituted.

When substituted alkenyls, alkynyls or cycloalkyls occur in the formula I, examples of suitable substituents are fluorine, chlorine or bromine.

When R² and R³ together with the nitrogen connecting them are a 5- to 7-membered saturated heterocyclic radical which can contain further hetero atoms, suitable examples are pyrrolidino, piperidino, morpholino, thiomorpholino, thiomorpholino S,S-dioxide, piperazino, N-(C₁ -C₄ -alkyl)piperazino or hexamethyleneimino.

Examples of R¹ are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, propinyl, methallyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2- or 3-hydroxypropyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-(2-phenoxyethoxy)propyl, 2- or 3-benzyloxypropyl, 2-methylthioethyl, 2-ethylthioethyl, 2- or 3-methylthiopropyl, 2- or 3-ethylthiopropyl, 2-aminoethyl, 2-(N,N-dimethylamino)ethyl, 2-(N,N-diethylamino)ethyl, 2- or 3-(N,N-dimethylamino)propyl, 2- or 3-(N,N-diethylamino)propyl, 2- or 3-aminopropyl, benzyl, 1-phenylethyl, 2-phenylethyl, phenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, pyrid-2-yl, pyrid-3-yl, pyrid-4-yl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-(3,4-dichlorophenyl)ethyl, diphenylmethyl, 2-(3-chloro-2-methylphenyl)ethyl, 2-(3,4-dimethoxyphenyl)ethyl, 2-(2-chlorophenyl)ethyl, amino, dimethylamino, diethylamino, thien-2-yl, 2-morpholinoethyl, 2- or 3-morpholinopropyl or 2-piperazinoylethyl. (The terms isooctyl, isononyl, isodecyl and isotridecyl used above are trivial names and derive from the alcohols obtained in the oxo synthesis--cf. in this connection Ullmanns Enzyklopadie der technischen Chemie, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436.

Examples of R² and R³ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or allyl.

Examples of R⁵ are chlorine, bromine, acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, hexanoyloxy or benzoyloxy.

Examples of R⁶ are methyl, ethyl, formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, benzoyl, chlorine or bromine.

--NX³ is derived from primary amines of the formula H₂ NX³. Examples of these which may be mentioned are methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, neopentylamine, hexylamine, heptylamine, n-octylamine, isooctylamine, 2-ethylhexylamine, nonylamine, isononylamine, decylamine, isodecylamine, undecylamine, dodecylamine, tridecylamine, isotridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine eicosylamine, allylamine, methallylamine, propargylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclononylamine, cyclodecylamine, 2-hydroxyethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-hydroxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-(2-phenoxyethoxy)propylamine, 3-benzyloxypropylamine, 2-(N,N-dimethylamino)ethylamine, 2-(N,N-diethylamino)ethylamine, 3-(N,N-dimethylamino)propylamine, 3-(N,N-diethylamino)propylamine, benzylamine, 2-phenylethylamine, 3-phenylpropylamine, aniline, 2-hydroxyaniline, 3-hydroxyaniline, 4-hydroxyaniline, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, 2-chloroaniline, 3-chloroaniline, 3-nitroaniline, 4-nitroaniline, o-toluidine, m-toluidine, p-toluidine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, glycine methyl ester, glycine ethyl ester, glycine propyl ester, glycine butyl ester, hydrazine, N,N-dimethylhydrazine or phenylhydrazine.

T⁵ is derived from active methylene compounds of the formula H₂ T⁵. Examples of such compounds are those of the formula ##STR9## where Z³ is hydrogen, cyano, nitro, C₁ -C₆ -alkanoyl, benzoyl, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, carboxyl, C₁ -C₄ -alkoxycarbonyl, carbamoyl or C₁ -C₄ -mono- or dialkylcarbamoyl, or of the formula ##STR10## Some particularly important compounds are, e.g.: ##STR11## Pyrrole derivatives of the formula Ia or Ib ##STR12## where R¹, R², R³ and R⁶ each have the abovementioned meanings, are advantageously prepared by reacting the compound of the formula II ##STR13## where R⁶ has the abovementioned meaning, and cat⊕ is a cation (e.g. an alkali metal ion or, preferably, a trialkylammonium ion), with an amine of the formula IIIa or IIIb ##STR14## where R¹, R² and R³ each have the abovementioned meanings.

The reaction is expediently carried out in an inert solvent (e.g. N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, hexamethylphosphoric trisamide, 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydropyrimidin-2-one or 1,2-diethoxyethane) in the presence of a base (e.g. triethylamine, tripropylamine, tributylamine, N-methylpiperidine or N,N-dimethylaniline) at from 0° to 150° C. The molar ratio of compound III to amine is 1:1 to 1:5 as a rule.

The compound of the formula II can be prepared in a conventional manner from malononitrile and the carbonyl chloride of the formula IV ##STR15## where R⁶ has the abovementioned meaning.

The pyrrole derivatives of the formula Ia and Ib can be reacted by conventional methods (e.g. by the Vilsmeier reaction) to give further compounds of the formula I.

Further details of the preparation can be taken from the Examples.

The novel pyrrole derivatives of the formula I are suitable, depending on the constitution, as diazo or coupling components for azo dyes.

Preferred pyrrole derivatives of the formula I are those where

R¹ is hydrogen, C₁ -C₁₅ -alkyl, C₅ -C₇ -cycloalkyl, C₃ -C₅ -alkenyl, C₂ C₅ -hydroxyalkyl, C₂ -C₅ -halogenoalkyl, C₁ -C₅ -alkoxy-C₂ -C₅ -alkyl, phenoxy-C₂ -C₅ -alkoxy-C₂ -C₅ -alkyl, phenyl-C₁ -C₅ -alkoxy-C₂ -C₅ -alkoxy-C₂ -C₅ -alkyl, C₁ -C₅ -alkylthio-C₂ -C₅ -alkyl, C₁ -C₅ -dialkylamino-C₂ -C₂ -alkyl, phenyl-C₁ -C₅ -alkyl, C₁ -C₅ -alkoxycarbonyl-C₁ C₅ -alkyl, --(CH₂)_(n) --Y where n is from 1 to 5 and Y is pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C₁ -C₄ -alkyl)piperazino or hexamethyleneimino, or phenyl, pyridyl, amino or C₁ -C₅ -dialkylamino,

R² is hydrogen, C₁ -C₄ -alkyl, allyl, benzyl or phenyl,

R³ is hydrogen, C₁ -C₄ -alkyl, allyl or benzyl, or R² and R³ together are ##STR16## where T¹ is hydrogen or C₁ -C₄ -alkyl, T² is C₁ -C₄ -alkyl or phenyl, and T³ is C₁ -C₄ -alkyl, or R² and R³ together with the nitrogen connecting them are pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C₁ -C₄ -alkyl)piperazino or hexamethyleneimino,

R⁴ is cyano, carbamoyl, thiocarbamoyl or ##STR17##

R⁵ is fluorine, chlorine, bromine, hydroxyl, C₁ -C₆ -alkanoyloxy or benzoyloxy and

R⁶ is hydrogen, C₁ -C₄ -alkyl, phenyl, C₁ -C₆ -alkanoyl, benzoyl, cyano, chlorine, bromine, nitro, hydroxysulfonyl or ##STR18## where T⁴ and T⁵ each have the abovementioned meanings.

Particularly preferred pyrrole derivatives of the formula I are those in which

R¹ is hydrogen, C₁ -C₁₀ -alkyl, C₃ -C₄ -alkenyl, benzyl, phenyl or amino,

R² is hydrogen, C₁ -C₄ -alkyl, allyl, benzyl or phenyl,

R³ is hydrogen C₁ -C₄ -alkyl or allyl, or R² and R³ together with the nitrogen connecting the nitrogen connecting them are pyrrolidino, piperidino, morpholino, thiomorpholino, N-methylpiperazino or hexamethyleneimino,

R⁴ is cyano, carbamoyl, thiocarbamoyl or ##STR19##

R⁵ is chlorine, bromine, hydroxyl, C₁ -C₆ -alkanoyloxy or benzoyloxy and

R⁶ is hydrogen, C₁ -C₄ -alkyl, phenyl, C₁ -C₆ -alkanoyl, benzoyl, cyano or ##STR20## where Z¹ and Z² are identical or different and, independently of one another, are each cyano, C₁ -C₄ -alkoxycarbonyl or nitro, and X³ has the abovementioned meaning.

Of special interest are pyrrole derivatives of the formula I where

R¹ is C₁ -C₄ -alkyl, phenyl or amino and

R² and R³ are each hydrogen or

R¹ is hydrogen,

R² is methyl, ethyl, allyl, benzyl or phenyl,

R³ is methyl, ethyl or allyl or R² and R³ together with the nitrogen connecting them are pyrrolidino, piperidino, morpholino, N-methylpiperazino or hexamethyleneimino,

R⁴ is cyano or carbamoyl,

R⁵ is chlorine, bromine or hydroxyl,

R⁶ is hydrogen, formyl, cyano or ##STR21## where Z¹ and Z² are identical or different and, independently of one another, are each cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl or nitro.

Particularly important pyrrole derivatives in this connection are those in which the radicals Z¹ and Z² are, independently of one another, cyano or C₁ -C₄ -alkoxycarbonyl or else one of the two radicals is hydrogen.

The Examples which follow are intended to illustrate the invention.

EXAMPLE 1 2-Amino-3-cyano-1-methyl-pyrrolin-4-one

99 g of malononitrile were dissolved in 150 ml of N,N-dimethylformamide (DMF) and cooled to 0° C. While cooling, 556 g of tributylamine and 169.5 g of chloroacetyl chloride were simultaneously added dropwise to this, and the mixture was then stirred at 10° C. for 10 minutes. The reaction mixture was subsequently added to a mixture of 1.5 kg of ice and 327 ml of 40% by weight aqueous methylamine solution and stirred at room temperature for 8 hours. The precipitate was filtered off with suction, washed and dried in an oven at 50° C. 124 g (60% of theory) of the compound of the formula ##STR22## of melting point 300° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

EXAMPLE 2 2-Amino-3-cyano-1-ethylpyrrolin-4-one

19.8 g of malononitrile were dissolved in 30 ml of DMF and cooled to 0° C. While cooling, 61 g of triethylamine and 32 g of chloroacetyl chloride were simultaneously added dropwise to this, and the mixture was then stirred at 10° C. for 10 minutes. Subsequently, while cooling, 49 g of 70% by weight aqueous ethylamine solution were added dropwise, and the mixture was stirred at room temperature for 8 hours. The precipitate was filtered off with suction, washed and dried at 50° C. 41.8 g (92%) of impure crude product were obtained and were recrystallized from 1:1 isopropanol/water with the addition of active carbon. This resulted in 10.9 g (24% of theory) of the compound of the formula ##STR23## of melting point 278° to 280° C. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

EXAMPLE 3 2-Amino-3-cyano-1-isopropylpyrrolin-4-one

99 g of malononitrile were dissolved in 150 ml of DMF and cooled to 0° C. While cooling, 306 g of triethylamine and 159 g of chloroacetyl chloride were simultaneously added dropwise to this. The reaction mixture was stirred at 10° C. for 10 minutes and subsequently added to a mixture of 1.5 kg of ice and 158 g of isopropylamine. The mixture was stirred at room temperature for 8 hours. The volatiles were then removed by distillation under atmospheric pressure at 100° C., and the distillation residue was cooled to 5° C. The precipitate was filtered off with suction, washed and dried. 105.6 g (43% of theory) of the compound of the formula ##STR24## of melting point 285° to 290° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

EXAMPLE 4 2-Amino-3-cyano-1-tridecylpyrrolin-4-one

19.8 g of malononitrile were dissolved in 30 ml of DMF and cooled to 0° C. While cooling, 61 g of triethylamine and 27 g of chloroacetyl chloride were simultaneously added dropwise to this, and the mixture was stirred at 10° C. for 10 minutes. 65.7 g of tridecylamine were then added dropwise, and the reaction mixture was stirred at room temperature for 48 hours. 300 ml of isopropylamine were then added to the mixture, which was refluxed for 2 hours, 10 g of active carbon were added, and the mixture was filtered hot. After cooling, the precipitate was filtered off with suction, washed and dried at 50° C. 40 g (44% of theory) of the compound of the formula ##STR25## of melting point 214° to 215° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

EXAMPLE 5 1-Allyl-2-amino-3-cyanopyrrolin-4-one

19.8 g of malononitrile were dissolved in 30 ml of DMF and cooled to 0° C. While cooling, 87 g of tributylamine and 27 g of chloroacetyl chloride were simultaneously added dropwise to this, and the mixture was stirred at 10° C. for 10 minutes. The mixture was then added to a mixture of 300 g of ice and 43 g of allylamine and stirred at room temperature for 8 hours. The precipitate was filtered off with suction, washed and dried. 38.1 g (78% of theory) of impure crude product were obtained and were boiled in 150 ml of isopropanol to purify. After cooling to 5° C., the precipitate was filtered off with suction, washed and dried. 31.2 g (64% of theory) of the compound of the formula ##STR26## of melting point 275° to 278° C. were obtained The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

EXAMPLE 6 2-cyano-3-cyano-1-(2-methoxyethyl)pyrrolin-4-one

99 g of malononitrile were dissolved in 150 ml of DMF and cooled to 0° C. While cooling, 306 g of triethylamine and 159 g of chloracetyl chloride were simultaneously added dropwise to this, and the mixture was stirred at 10° C. for 10 minutes. The mixture was then added to a mixture of 1.5 kg of ice and 291 g of 2-methoxyethylamine and stirred at room temperature for 8 hours. The volatiles were removed by distillation at 100° C. under atmospheric pressure, and the distillation residue was concentrated in a rotary evaporator at the water pump. The residue was recrystallized from 500 ml of isopropanol. The precipitate was filtered off with suction, washed and dried at 50° C. 205.5 g (76% of theory) of the compound of the formula ##STR27## of melting point 108° to 110° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

EXAMPLE 7 2-Amino-3-cyano-1-phenylpyrrolin-4-one Variant A

26.4 g of malononitrile were dissolved in 150 ml of DMF and cooled to 0° C. While cooling, 148 g of tributylamine and 45 g of chloracetyl chloride were simultaneously added dropwise to this, and the mixture was stirred at room temperature for 30 minutes. 42 g of aniline were then added to the mixture, which was stirred at 80° C. for 15 hours and then 200 g of water were added. After cooling to room temperature, the organic phase was separated off and digested with dichloromethane. The precipitate was filtered off with suction, washed and dried. 37.4 g (46% of theory) of the compound of the formula ##STR28## of melting point 285° to 290° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula

Variant B

19.8 g of malononitrile were dissolved in 30 ml of DMF and cooled to 0° C. While cooling, 61 g of triethylamine and 27 g of chloracetyl chloride were simultaneously added dropwise to this, and the mixture was stirred at 10° C. for 10 minutes. 27.6 g of aniline were then added, and the reaction mixture was stirred at room temperature for 8 hours. 1 kg of water was added, and the mixture was then refluxed for 2 hours and cooled to 10° C., and the precipitate was filtered off with suction, washed and dried. 39.2 g (66% of theory) of the compound identical in all data to the product synthesized in Variant A) were obtained. The compounds listed in the following Table 1 are obtained in a similar manner.

                                      TABLE 1                                      __________________________________________________________________________      ##STR29##                                                                     Example                           Melting point                                No.  L.sup.1         L.sup.2   L.sup.3                                                                           [°C.]                                 __________________________________________________________________________     8    CH.sub.2CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                     NH.sub.2  H                                               9    n-C.sub.3 H.sub.7                                                                              NH.sub.2  H  257-267                                      10   n-C.sub.4 H.sub.9                                                                              NH.sub.2  H  182-192                                      11   iso-C.sub.4 H.sub.9                                                                            NH.sub.2  H                                               12   sec-C.sub.4 H.sub.9                                                                            NH.sub.2  H                                               13   n-C.sub.5 H.sub.11                                                                             NH.sub.2  H                                               14   Neo-C.sub.5 H.sub.11                                                                           NH.sub.2  H                                               15   n-C.sub.6 H.sub.13                                                                             NH.sub.2  H                                               16   n-C.sub.7 H.sub.15                                                                             NH.sub.2  H                                               17   n-C.sub.8 H.sub.17                                                                             NH.sub.2  H                                               18   n-C.sub.9 H.sub.19                                                                             NH.sub.2  H                                               19   n-C.sub.10 H.sub.21                                                                            NH.sub.2  H                                               20   n-C.sub.11 H.sub.23                                                                            NH.sub.2  H                                               21   n-C.sub.12 H.sub.25                                                                            NH.sub.2  H                                               22   n-C.sub.14 H.sub.29                                                                            NH.sub.2  H                                               23   n-C.sub.15 H.sub.31                                                                            NH.sub.2  H                                               24   n-C.sub.16 H.sub.33                                                                            NH.sub.2  H                                               25   n-C.sub.17 H.sub.35                                                                            NH.sub.2  H                                               26   n-C.sub.18 H.sub.37                                                                            NH.sub.2  H                                               27   n-C.sub.19 H.sub.39                                                                            NH.sub.2  H                                               28   n-C.sub.20 H.sub.41                                                                            NH.sub.2  H                                               29   CH.sub.2 CCH    NH.sub.2  H                                               30   Cyclo-C.sub.3 H.sub.5                                                                          NH.sub.2  H                                               31   Cyclo-C.sub.4 H.sub.7                                                                          NH.sub.2  H                                               32   Cyclo-C.sub.5 H.sub.9                                                                          NH.sub.2  H                                               33   Cyclo-C.sub.6 H.sub.11                                                                         NH.sub.2  H  300                                          34   Cyclo-C.sub.7 H.sub.13                                                                         NH.sub.2  H                                               35   Cyclo-C.sub.8 H.sub.15                                                                         NH.sub.2  H                                               36   Cyclo-C.sub.9 H.sub.17                                                                         NH.sub.2  H                                               37   Cyclo-C.sub.10 H.sub.19                                                                        NH.sub.2  H                                               38   CH.sub.2 CH.sub.2 OH                                                                           NH.sub.2  H  245-250                                      39   CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                             NH.sub.2  H                                               40   CH.sub.2 CH.sub.2 NH.sub.2                                                                     NH.sub.2  H                                               41   CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                            NH.sub.2  H                                               42   CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                     NH.sub.2  H                                               43   CH.sub.2 CH.sub.2 SCH.sub.3                                                                    NH.sub.2  H                                               44   CH.sub.2 CH.sub. 2 SC.sub.2 H.sub.5                                                            NH.sub.2  H                                               45   (CH.sub.2).sub.3 OH                                                                            NH.sub.2  H                                               46   (CH.sub.2).sub.3 OCH.sub.3                                                                     NH.sub.2  H                                               47   (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                              NH.sub.2  H                                               48   (CH.sub.2).sub.3 NH.sub.2                                                                      NH.sub.2  H                                               49   (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                             NH.sub.2  H                                               50   (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                      NH.sub.2  H                                               51   (CH.sub.2).sub.3 SCH.sub.3                                                                     NH.sub.2  H                                               52   (CH.sub.2).sub.3 SC.sub.2 H.sub.5                                                              NH.sub.2  H                                               53   CH.sub.2 C.sub.6 H.sub.5                                                                       NH.sub.2  H  236-238                                      54   CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  H  230-232                                      55   CH(CH.sub.3)C.sub.6 H.sub.5                                                                    NH.sub.2  H                                               56   CH(C.sub.6 H.sub.5).sub.2                                                                      NH.sub.2  H                                               57   C.sub.6 H.sub.4 -(2)-OH                                                                        NH.sub.2  H                                               58   C.sub.6 H.sub.4 -(3)-OH                                                                        NH.sub.2  H                                               59   C.sub.6 H.sub.4 -(4)-OH                                                                        NH.sub.2  H                                               60   C.sub.6 H.sub.4 -(2)-OCH.sub.3                                                                 NH.sub.2  H                                               61   C.sub.6 H.sub.4 -(3)-OCH.sub.3                                                                 NH.sub.2  H  234                                          62   C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                 NH.sub.2  H  270                                          63   C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5                                                          NH.sub.2  H                                               64   C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5                                                          NH.sub.2  H                                               65   C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5                                                          NH.sub.2  H                                               66   C.sub.6 H.sub.4 -(2)-Cl                                                                        NH.sub.2  H                                               67   C.sub.6 H.sub.4 -(3)-Cl                                                                        NH.sub.2  H                                               68   C.sub.6 H.sub.4 -(4)-Cl                                                                        NH.sub.2  H                                               69   C.sub.6 H.sub.4 -(2)-NO.sub.2                                                                  NH.sub.2  H                                               70   C.sub.6 H.sub.4 -(3)-NO.sub.2                                                                  NH.sub.2  H                                               71   C.sub.6 H.sub.4 -(4)-NO.sub.2                                                                  NH.sub.2  H                                               72   C.sub.6 H.sub.4 -(2)-NH.sub.2                                                                  NH.sub.2  H                                               73   C.sub.6 H.sub.4 -(3)-NH.sub.2                                                                  NH.sub.2  H                                               74   C.sub.6 H.sub.4 -(4)-NH.sub.2                                                                  NH.sub.2  H                                               75   C.sub.6 H.sub.4 -(2)-CH.sub.3                                                                  NH.sub.2  H                                               76   C.sub.6 H.sub.4 -(3)-CH.sub.3                                                                  NH.sub.2  H                                               77   C.sub.6 H.sub.4 -(4)-CH.sub.3                                                                  NH.sub.2  H                                               78   C.sub.6 H.sub.4 -(2)-C.sub.2 H.sub.5                                                           NH.sub.2  H                                               79   C.sub.6 H.sub.4 -(3)-C.sub.2 H.sub.5                                                           NH.sub.2  H                                               80   C.sub.6 H.sub.4 -(4)-C.sub.2 H.sub.5                                                           NH.sub.2  H                                               81   C.sub.6 H.sub.4 -(2)-CN                                                                        NH.sub.2  H                                               82   C.sub.6 H.sub.4 -(3)-CN                                                                        NH.sub.2  H                                               83   C.sub.6 H.sub.4 -(4)-CN                                                                        NH.sub.2  H                                               84   C.sub.6 H.sub.4 -(2)-COOCH.sub.3                                                               NH.sub.2  H                                               85   C.sub.6 H.sub.4 -(3)-COOCH.sub.3                                                               NH.sub.2  H                                               86   C.sub.6 H.sub.4 -(4)-COOCH.sub.3                                                               NH.sub.2  H                                               87   Pyrid-2-yl      NH.sub.2  H                                               88   Pyrid-3-yl      NH.sub.2  H  300                                          89   Pyrid-4-yl      NH.sub.2  H                                               90   (CH.sub.2).sub.2C.sub.6 H.sub.3 -(3)-Cl(2)-CH.sub.3                                            NH.sub.2  H  270                                          91   (CH.sub.2).sub.2C.sub.6 H.sub.3 -(3,4)-(OCH.sub.3).sub.2                                       NH.sub.2  H  220-225                                      92   (CH.sub.2).sub.2C.sub.6 H.sub.4 -(2)-Cl                                                        NH.sub.2  H  above 270                                    93   C.sub.6 H.sub.3 -(3,4)-Cl.sub.2                                                                NH.sub.2  H  above 270                                    94   CH.sub.2COOCH.sub.3                                                                            NH.sub.2  H  above 270                                    95   CH.sub.2COOC.sub.2 H.sub.5                                                                     NH.sub.2  H                                               96   NH.sub.2        NH.sub.2  H  280-285                                      97   N(CH.sub.3).sub.2                                                                              NH.sub.2  H                                               98   N(C.sub.2 H.sub.5).sub.2                                                                       NH.sub.2  H                                               99   H               N(CH.sub.3).sub.2                                                                        H  228-235                                      100  H               N(C.sub.2 H.sub.5).sub.2                                                                 H  119-123                                      101  H               N(n-C.sub.3 H.sub.7).sub.2 2                                                             H                                               102  H               N(n-C.sub.4 H.sub.9).sub.2 2                                                             H                                               103  H                                                                                               ##STR30##                                                                               H  245-249                                      104  H                                                                                               ##STR31##                                                                               H  267-269                                      105  H                                                                                               ##STR32##                                                                               H                                               106  H                                                                                               ##STR33##                                                                               H  280-284                                      107  H                                                                                               ##STR34##                                                                               H                                               108  H                                                                                               ##STR35##                                                                               H                                               109  CH.sub.3        NH.sub.2  CH.sub.3                                                                          298                                          110  C.sub.2 H.sub.5 NH.sub.2  CH.sub.3                                        111  iso-C.sub.3 H.sub.7                                                                            NH.sub.2  CH.sub.3                                        112  CH.sub.2 CHCH.sub.2                                                                            NH.sub.2  CH.sub.3                                        113  Cyclo-C.sub.6 H.sub.11                                                                         NH.sub.2  CH.sub.3                                        114  CH.sub.2 CH.sub.2 OH                                                                           NH.sub.2  CH.sub.3                                        115  CH.sub.2 CH.sub.2 OCH.sub.3                                                                    NH.sub.2  CH.sub.3                                        116  CH.sub.2 C.sub.6 H.sub.5                                                                       NH.sub.2  CH.sub.3                                        117  C.sub.6 H.sub.5 NH.sub.2  CH.sub.3                                        118  C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                 NH.sub.2  CH.sub.3                                        119  C.sub.6 H.sub.4 -(2)-CH.sub.3                                                                  NH.sub.2  CH.sub.3                                        120  Pyrid-3-yl      NH.sub.2  CH.sub.3                                        121  NH.sub.2        NH.sub.2  CH.sub.3                                        122  H               N(CH.sub.3).sub.2                                                                        CH.sub.3                                        123  H               N(C.sub.2 H.sub.5).sub.2                                                                 CH.sub.3                                        124  H                                                                                               ##STR36##                                                                               CH.sub.3                                        125  H                                                                                               ##STR37##                                                                               CH.sub.3                                        126  CH.sub.3        NH.sub.2  C.sub.6 H.sub.5                                 127  C.sub.2 H.sub.5 NH.sub.2  C.sub.6 H.sub.5                                 128  iso-C.sub.3 H.sub.7                                                                            NH.sub.2  C.sub.6 H.sub.5                                 129  CH.sub.2 CHCH.sub.2                                                                            NH.sub.2  C.sub.6 H.sub.5                                 130  CH.sub.2 CH.sub.2 OH                                                                           NH.sub.2  C.sub.6 H.sub.5                                 131  CH.sub.2 CH.sub.2 OCH.sub.3                                                                    NH.sub.2  C.sub.6 H.sub.5                                 132  CH.sub.2 C.sub.6 H.sub.5                                                                       NH.sub.2  C.sub.6 H.sub.5                                 133  C.sub.6 H.sub.5 NH.sub.2  C.sub.6 H.sub.5                                 134  C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                 NH.sub.2  C.sub.6 H.sub.5                                 135  C.sub.6 H.sub.4 -(4)-CN                                                                        NH.sub.2  C.sub.6 H.sub.5                                 136  NH.sub.2        NH.sub.2  C.sub.6 H.sub.5                                 137  H               N(CH.sub.3).sub.2                                                                        C.sub.6 H.sub.5                                 138  H               N(C.sub.2 H.sub.5).sub.2                                                                 C.sub.6 H.sub.5                                 139  H                                                                                               ##STR38##                                                                               C.sub.6 H.sub.5                                 140  H                                                                                               ##STR39##                                                                               C.sub.6 H.sub.5                                 141  (CH.sub.2).sub.3OCH.sub.2 C.sub.6 H.sub.5                                                      NH.sub.2  H  149                                          142  (CH.sub.2).sub.3O(CH.sub.2).sub.2OC.sub.6 H.sub.5                                              NH.sub.2  H  132                                          __________________________________________________________________________

EXAMPLE 143 4-Chloro-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole

364 ml of phosphoryl chloride (POCl₃) were added dropwise at 0° to 5° C. to 1.5 1 of DMF. After one hour at 0° to 5° C., a solution of 137 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1) in 1.5 1 of DMF was added dropwise to the reaction mixture (exothermic reaction with temperature rising to 40° C.). After the mixture had been stirred at 100° C. for 4 hours, it was cooled to room temperature, hydrolyzed with 5 l of water and adjusted to pH 8 to 9 with 50% concentrated sodium hydroxide solution. The beige-colored precipitate was filtered off with suction and dried in an oven at 50° C. 180 g (75% of theory) of the compound of the formula ##STR40## of melting point 150° to 152° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

EXAMPLE 144 4-Bromo-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole

172 g of phosphoryl bromide (POBr₃) were added dropwise at 0° to 10° C. to 200 ml of DMF. The mixture was stirred for 5 minutes and then a further 100 ml of DMF were added. 27.4 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1) were introduced a little at a time into the cooled mixture. After the exothermic reaction had subsided, the reaction solution was stirred at 70° C. for 2 hours and then poured into 2 kg of ice-water. The suspension was stirred at room temperature for 8 hours. The precipitate was then filtered off with suction, washed and dried in an oven at 50° C. 12.6 g (22%) of the compound of the formula ##STR41## of melting point 180° to 184° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

The compounds listed in Table 2 are obtained in a similar manner.

                  TABLE 2                                                          ______________________________________                                          ##STR42##                                                                     Example                             Melting point                              No.    L.sup.1           L.sup.2                                                                              L.sup.3                                                                             [°C.]                               ______________________________________                                         145    C.sub.2 H.sub.5   Cl    CHO                                             146    n-C.sub.3 H.sub.7 Cl    CHO                                             147    iso-C.sub.3 H.sub.7                                                                              Cl    CHO  136-139                                    148    n-C.sub.4 H.sub.9 Cl    CHO                                             149    iso-C.sub.4 H.sub.9                                                                              Cl    CHO                                             150    sec-C.sub.4 H.sub.9                                                                              Cl    CHO                                             151    n-C.sub.5 H.sub.11                                                                               Cl    CHO                                             152    Neo-C.sub.5 H.sub.11                                                                             Cl    CHO                                             153    n-C.sub.6 H.sub.13                                                                               Cl    CHO                                             154    n-C.sub.7 H.sub.15                                                                               Cl    CHO                                             155    n-C.sub.8 H.sub.17                                                                               Cl    CHO                                             156    n-C.sub.9 H.sub.19                                                                               Cl    CHO                                             157    n-C.sub.10 H.sub.21                                                                              Cl    CHO                                             158    n-C.sub.11 H.sub.23                                                                              Cl    CHO                                             159    n-C.sub.12 H.sub.25                                                                              Cl    CHO                                             160    n-C.sub.13 H.sub.27                                                                              Cl    CHO                                             161    n-C.sub.14 H.sub.29                                                                              Cl    CHO                                             162    n-C.sub.15 H.sub.31                                                                              Cl    CHO                                             163    n-C.sub. 16 H.sub.33                                                                             Cl    CHO                                             164    n-C.sub.17 H.sub.35                                                                              Cl    CHO                                             165    n-C.sub.18 H.sub.37                                                                              Cl    CHO                                             166    n-C.sub.19 H.sub.39                                                                              Cl    CHO                                             167    n-C.sub.20 H.sub.41                                                                              Cl    CHO                                             168    Cyclo-C.sub.3 H.sub.5                                                                            Cl    CHO                                             169    Cyclo-C.sub.4 H.sub.7                                                                            Cl    CHO                                             170    Cyclo-C.sub.5 H.sub.9                                                                            Cl    CHO                                             171    Cyclo-C.sub.6 H.sub.11                                                                           Cl    CHO                                             172    Cyclo-C.sub.7 H.sub.13                                                                           Cl    CHO                                             173    Cyclo-C.sub.8 H.sub.15                                                                           Cl    CHO                                             174    Cyclo-C.sub.9 H.sub.17                                                                           Cl    CHO                                             175    Cyclo-C.sub.10 H.sub.19                                                                          Cl    CHO                                             176    CH.sub.2 CH.sub.2 Cl                                                                             Cl    CHO  119-123                                    177    CH.sub.2 CH.sub.2 OCH.sub.3                                                                      Cl    CHO                                             178    CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                               Cl    CHO                                             179    CH.sub.2 CH.sub.2 NCHN(CH.sub.3).sub.2                                                           Cl    CHO                                             180    CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                              Cl    CHO                                             181    CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       Cl    CHO                                             182    CH.sub.2 CH.sub.2 SCH.sub.3                                                                      Cl    CHO                                             183    CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                               Cl    CHO                                             184    (CH.sub.2).sub.3 Cl                                                                              Cl    CHO                                             185    (CH.sub.2).sub.3 OCH.sub.3                                                                       Cl    CHO                                             186    (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                                Cl    CHO                                             187    (CH.sub.2).sub.3 NCHN(CH.sub.3).sub.2                                                            Cl    CHO                                             188    (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                               Cl    CHO                                             189    (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                        Cl    CHO                                             190    (CH.sub.2).sub.3 SCH.sub.3                                                                       Cl    CHO                                             191    (CH.sub.2).sub.3 SC.sub.2 H.sub.5                                                                Cl    CHO                                             192    CH.sub.2 C.sub.6 H.sub.5                                                                         Cl    CHO                                             193    CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                                Cl    CHO                                             194    CH(CH.sub.3)C.sub.6 H.sub.5                                                                      Cl    CHO                                             195    CH(C.sub.6 H.sub.5).sub.2                                                                        Cl    CHO                                             196    C.sub.6 H.sub.5   Cl    CHO  175-176                                    197    C.sub.6 H.sub.4 -(2)-Cl                                                                          Cl    CHO                                             198    C.sub.6 H.sub.4 -(3)-Cl                                                                          Cl    CHO                                             199    C.sub.6 H.sub.4 -(4)-Cl                                                                          Cl    CHO                                             200    C.sub.6 H.sub.4 -(2)-OCH.sub.3                                                                   Cl    CHO                                             201    C.sub.6 H.sub.4 -(3)-OCH.sub.3                                                                   Cl    CHO  123-130                                    202    C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                   Cl    CHO  140-146                                    203    C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5                                                            Cl    CHO                                             204    C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5                                                            Cl    CHO                                             205    C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5                                                            Cl    CHO                                             206    C.sub.6 H.sub. 4 -(2)-NO.sub.2                                                                   Cl    CHO                                             207    C.sub.6 H.sub.4 -(3)-NO.sub.2                                                                    Cl    CHO                                             208    C.sub.6 H.sub.4 -(4)-NO.sub.2                                                                    Cl    CHO                                             209    CH.sub.2COOCH.sub.3                                                                              Cl    CHO                                             210    CH.sub.2COOC.sub.2 H.sub.5                                                                       Cl    CHO                                             211    NCHN(CH.sub.3).sub.2                                                                             Cl    CHO  183                                        212    N(CH.sub.3).sub.2 Cl    CHO                                             213    N(C.sub.2 H.sub.5).sub.2                                                                         Cl    CHO                                             214    C.sub.2 H.sub.5   Br    CHO                                             215    n-C.sub.3 H.sub.7 Br    CHO                                             216    iso-C.sub.3 H.sub.7                                                                              Br    CHO                                             217    n-C.sub.4 H.sub.9 Br    CHO                                             218    n-C.sub.13 H.sub.27                                                                              Br    CHO                                             219    Cyclo-C.sub.6 H.sub.11                                                                           Br    CHO                                             220    C.sub.6 H.sub.5   Br    CHO                                             221    C.sub.2 H.sub.4 Br                                                                               Br    CHO                                             222    NCHN(CH.sub.3).sub.2                                                                             Br    CHO                                             223    N(CH.sub.3).sub.2 Br    CHO                                             224    N(C.sub.2 H.sub.5).sub.2                                                                         Br    CHO                                             225    CH.sub.3          Cl    CH.sub.3                                        226    C.sub.2 H.sub.5   Cl    CH.sub.3                                        227    iso-C.sub.3 H.sub.7                                                                              Cl    CH.sub.3                                        228    CH.sub.2 CHCH.sub.2                                                                              Cl    CH.sub.3                                        229    Cyclo-C.sub.6 H.sub.11                                                                           Cl    CH.sub.3                                        230    CH.sub.2 CH.sub.2 Cl                                                                             Cl    CH.sub.3                                        231    CH.sub.2 CH.sub.2 OCH.sub.3                                                                      Cl    CH.sub.3                                        232    CH.sub.2 C.sub.6 H.sub.5                                                                         Cl    CH.sub.3                                        233    C.sub.6 H.sub.5   Cl    CH.sub.3                                        234    Pyrid-3-yl        Cl    CH.sub.3                                        235    CH.sub.3          Br    CH.sub.3                                        236    C.sub.2 H.sub.5   Br    CH.sub.3                                        237    iso-C.sub.3 H.sub.7                                                                              Br    CH.sub.3                                        238    CH.sub.2 CHCH.sub.2                                                                              Br    CH.sub.3                                        239    Cyclo-C.sub.6 H.sub.11                                                                           Br    CH.sub.3                                        240    CH.sub.2 CH.sub.2 Br                                                                             Br    CH.sub.3                                        241    CH.sub.2 CH.sub.2 OCH.sub.3                                                                      Br    CH.sub.3                                        242    CH.sub.2 C.sub.6 H.sub.5                                                                         Br    CH.sub.3                                        243    C.sub.6 H.sub.5   Br    CH.sub.3                                        244    Pyrid-3-yl        Br    CH.sub.3                                        245    CH.sub.3          Cl    C.sub.6 H.sub.5                                 246    C.sub.2 H.sub.5   Cl    C.sub.6 H.sub.5                                 247    iso-C.sub.3 H.sub.7                                                                              Cl    C.sub.6 H.sub.5                                 248    CH.sub.2 CHCH.sub.2                                                                              Cl    C.sub.6 H.sub.5                                 249    Cyclo-C.sub.6 H.sub.11                                                                           Cl    C.sub.6 H.sub.5                                 250    CH.sub.2 CH.sub.2 Cl                                                                             Cl    C.sub.6 H.sub.5                                 251    CH.sub.2 CH.sub.2 OCH.sub.3                                                                      Cl    C.sub.6 H.sub.5                                 252    CH.sub.2 C.sub.6 H.sub.5                                                                         Cl    C.sub.6 H.sub.5                                 253    C.sub.6 H.sub.5   Cl    C.sub. 6 H.sub.5                                254    Pyrid-3-yl        Cl    C.sub.6 H.sub.5                                 255    CH.sub.3          Br    C.sub.6 H.sub.5                                 256    C.sub.2 H.sub.5   Br    C.sub.6 H.sub.5                                 257    iso-C.sub.3 H.sub.7                                                                              Br    C.sub.6 H.sub.5                                 258    CH.sub.2 CHCH.sub.2                                                                              Br    C.sub.6 H.sub.5                                 259    Cyclo-C.sub.6 H.sub.11                                                                           Br    C.sub.6 H.sub.5                                 260    CH.sub.2 CH.sub.2 Br                                                                             Br    C.sub.6 H.sub.5                                 261    CH.sub.2 CH.sub.2 OCH.sub.3                                                                      Br    C.sub.6 H.sub.5                                 262    CH.sub.2 C.sub.6 H.sub.5                                                                         Br    C.sub.6 H.sub.5                                 263    C.sub.6 H.sub.5   Br    C.sub.6 H.sub.5                                 264    Pyrid-3-yl        Br    C.sub.6 H.sub.5                                 ______________________________________                                    

EXAMPLE 265 4-Chloro-3-cyano-2-dimethylformamidino-1-methylpyrrole

33 ml of phosphoryl chloride (POCl₃) were added dropwise at 0° to 5° C. to 285 ml of DMF. After 1 hour at 0° to 5° C., 41.1 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1) were added a little at a time to the reaction solution (exothermic reaction with temperature rising to 40° C.). After the mixture had been stirred at 70° C. for 1 hour it was cooled to room temperature, hydrolyzed with 1.5 l of water and adjusted to pH 7 with 240 g of sodium acetate. The precipitate was filtered off with suction and dried in an oven at 50° C. 40.5 g (75% of theory) of the compound of the formula ##STR43## of melting point 88° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

EXAMPLE 266 4-Bromo-3-cyano-2-dimethylformamidino-1-methylpyrrole

70 g of phosphoryl bromide (POBr₃) were added dropwise at 0° to 10° C. to 190 ml of DMF. After one hour at 0° to 5° C., 27 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1) were added a little at a time to the reaction solution (exothermic reaction with temperature rising to 30° C.). After the mixture had been stirred at 80° C. for 1 hour it was cooled to room temperature, hydrolyzed with 1.5 l of water and adjusted to pH 7 with 160 g of sodium acetate. The precipitate was filtered off with suction and dried in an oven at 50° C. 22.5 g (44% of theory) of the compound of the formula ##STR44## were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

The compounds listed in the following Table 3 are obtained in a similar manner.

                  TABLE 3                                                          ______________________________________                                          ##STR45##                                                                     Example                           Melting point                                No.     L.sup.1            L.sup.2                                                                               [°C.]                                 ______________________________________                                         267     C.sub.2 H.sub.5    Cl                                                  268     n-C.sub.3 H.sub.7  Cl                                                  269     iso-C.sub.3 H.sub.7                                                                               Cl                                                  270     n-C.sub.4 H.sub.9  Cl                                                  271     iso-C.sub.4 H.sub.9                                                                               Cl                                                  272     sec-C.sub.4 H.sub.9                                                                               Cl                                                  273     n-C.sub.5 H.sub.11 Cl                                                  274     Neo-C.sub.5 H.sub.11                                                                              Cl                                                  275     n-C.sub.6 H.sub.13 Cl                                                  276     n-C.sub.7 H.sub.15 Cl                                                  277     n-C.sub.8 H.sub.17 Cl                                                  278     n-C.sub.9 H.sub.19 Cl                                                  279     n-C.sub.10 H.sub.21                                                                               Cl                                                  280     n-C.sub.11 H.sub.23                                                                               Cl                                                  281     n-C.sub.12 H.sub.25                                                                               Cl                                                  282     n-C.sub.13 H.sub.27                                                                               Cl                                                  283     n-C.sub.14 H.sub.29                                                                               Cl                                                  284     n-C.sub.15 H.sub.31                                                                               Cl                                                  285     n-C.sub.16 H.sub.33                                                                               Cl                                                  286     n-C.sub.17 H.sub.35                                                                               Cl                                                  287     n-C.sub.18 H.sub.37                                                                               Cl                                                  288     n-C.sub.19 H.sub.39                                                                               Cl                                                  289     n-C.sub.20 H.sub. 41                                                                              Cl                                                  290     Cyclo-C.sub.3 H.sub.5                                                                             Cl                                                  291     Cyclo-C.sub.4 H.sub.7                                                                             Cl                                                  292     Cyclo-C.sub.5 H.sub.9                                                                             Cl                                                  293     Cyclo-C.sub.6 H.sub.11                                                                            Cl                                                  294     Cyclo-C.sub.7 H.sub.13                                                                            Cl                                                  295     Cyclo-C.sub.8 H.sub.15                                                                            Cl                                                  296     Cyclo-C.sub.9 H.sub.17                                                                            Cl                                                  297     Cyclo-C.sub.10 H.sub.19                                                                           Cl                                                  298     CH.sub.2 CH.sub.2 Cl                                                                              Cl                                                  299     CH.sub.2 CH.sub.2 OCH.sub.3                                                                       Cl                                                  300     CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                                Cl                                                  301     CH.sub.2 CH.sub.2 NCHN(CH.sub.3).sub.2                                                            Cl                                                  302     CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                               Cl                                                  303     CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        Cl                                                  304     CH.sub.2 CH.sub.2 SCH.sub.3                                                                       Cl                                                  305     CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                                Cl                                                  306     (CH.sub.2).sub.3 Cl                                                                               Cl                                                  307     (CH.sub.2).sub.3 OCH.sub.3                                                                        Cl                                                  308     (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                                 Cl                                                  309     (CH.sub.2).sub.3 NCHN(CH.sub.3).sub.2                                                             Cl                                                  310     (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                                Cl                                                  311     (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                         Cl                                                  312     (CH.sub.2).sub.3 SCH.sub.3                                                                        Cl                                                  313     (CH.sub.2).sub.3 SC.sub. 2 H.sub.5                                                                Cl                                                  314     CH.sub.2 C.sub.6 H.sub.5                                                                          Cl                                                  315     CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                                 Cl                                                  316     CH(CH.sub.3)C.sub.6 H.sub.5                                                                       Cl                                                  317     CH(C.sub.6 H.sub.5).sub.2                                                                         Cl                                                  318     C.sub.6 H.sub.5    Cl                                                  319     C.sub.6 H.sub.4 -(2)-Cl                                                                           Cl                                                  320     C.sub.6 H.sub.4 -(3)-Cl                                                                           Cl                                                  321     C.sub.6 H.sub.4 -(4)-Cl                                                                           Cl                                                  322     C.sub.6 H.sub.4 -(2)-OCH.sub.3                                                                    Cl                                                  323     C.sub.6 H.sub.4 -(3)-OCH.sub.3                                                                    Cl                                                  324     C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                    Cl                                                  325     C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5                                                             Cl                                                  326     C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5                                                             Cl                                                  327     C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5                                                             Cl                                                  328     C.sub.6 H.sub.4 -(2)-NO.sub.2                                                                     Cl                                                  329     C.sub.6 H.sub.4 -(3)-NO.sub.2                                                                     Cl                                                  330     C.sub.6 H.sub.4 -(4)-NO.sub.2                                                                     Cl                                                  331     CH.sub.2COOCH.sub.3                                                                               Cl                                                  332     CH.sub.2COOC.sub.2 H.sub.5                                                                        Cl                                                  333     NCHN(CH.sub.3).sub.2                                                                              Cl                                                  334     N(CH.sub.3).sub.2  Cl                                                  335     N(C.sub.2 H.sub.5).sub.2                                                                          Cl                                                  336     C.sub.2 H.sub.5    Br                                                  337     iso-C.sub.3 H.sub.7                                                                               Br                                                  338     Cyclo-C.sub.6 H.sub.11                                                                            Br                                                  339     CH.sub.2 CH.sub.2 Br                                                                              Br                                                  340     CH.sub.2 C.sub.6 H.sub.5                                                                          Br                                                  341     C.sub.6 H.sub.5    Br                                                  342     NCHN(CH.sub.3).sub.2                                                                              Br                                                  343     N(CH.sub.3).sub.2  Br                                                  344     N(C.sub.2 H.sub.5).sub.2                                                                          Br                                                  ______________________________________                                    

EXAMPLE 345 2-Amino-4-chloro-3-cyano-5-formyl-1-methylpyrrole

84.8 g of 4-chloro-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole (Example 143) were dissolved in 50 ml of water and 150 ml of ethanol. To this was added a solution of 15 g of KOH in 150 ml of ethanol, and the mixture was refluxed for 10 minutes. It was then poured into 1 kg of ice-water, the pH was adjusted to 7 with concentrated formic acid, and the precipitate was filtered off with suction, washed and dried in an oven at 50° C. 60.2 g (92% of theory) of the compound of the formula ##STR46## of melting point 282° to 285° C. are obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

The compounds listed in Table 4 are obtained in a similar manner to Example 345.

                  TABLE 4                                                          ______________________________________                                          ##STR47##                                                                     Example                            Melting point                               No.    L.sup.1        L.sup.2                                                                               L.sup.3                                                                              [°C.]                                ______________________________________                                         346    C.sub.2 H.sub.5                                                                               Cl     CHO                                               347    n-C.sub.3 H.sub.7                                                                             Cl     CHO                                               348    iso-C.sub.3 H.sub.7                                                                           Cl     CHO   180-195                                     349    n-C.sub.4 H.sub.9                                                                             Cl     CHO                                               350    iso-C.sub.4 H.sub.9                                                                           Cl     CHO                                               351    sec-C.sub.4 H.sub.9                                                                           Cl     CHO                                               352    n-C.sub.5 H.sub.11                                                                            Cl     CHO                                               353    Neo-C.sub.5 H.sub.11                                                                          Cl     CHO                                               354    n-C.sub.6 H.sub.13                                                                            Cl     CHO                                               355    n-C.sub.7 H.sub.15                                                                            Cl     CHO                                               356    n-C.sub.8 H.sub.17                                                                            Cl     CHO                                               357    n-C.sub.9 H.sub.19                                                                            Cl     CHO                                               358    n-C.sub.10 H.sub.21                                                                           Cl     CHO                                               359    n-C.sub.11 H.sub.23                                                                           Cl     CHO                                               360    n-C.sub.12 H.sub.25                                                                           Cl     CHO                                               361    n-C.sub.13 H.sub.27                                                                           Cl     CHO                                               362    n-C.sub.14 H.sub.29                                                                           Cl     CHO                                               363    n-C.sub.15 H.sub.31                                                                           Cl     CHO                                               364    n-C.sub.16 H.sub.33                                                                           Cl     CHO                                               365    n-C.sub.17 H.sub.35                                                                           Cl     CHO                                               366    n-C.sub.18 H.sub.37                                                                           Cl     CHO                                               367    n-C.sub.19 H.sub.39                                                                           Cl     CHO                                               368    n-C.sub.20 H.sub.41                                                                           Cl     CHO                                               369    Cyclo-C.sub.3 H.sub.5                                                                         Cl     CHO                                               370    Cyclo-C.sub.4 H.sub.7                                                                         Cl     CHO                                               371    Cyclo-C.sub.5 H.sub.9                                                                         Cl     CHO                                               372    Cyclo-C.sub.6 H.sub.11                                                                        Cl     CHO                                               373    Cyclo-C.sub.7 H.sub.13                                                                        Cl     CHO                                               374    Cyclo-C.sub.8 H.sub.15                                                                        Cl     CHO                                               375    Cyclo-C.sub.9 H.sub.17                                                                        Cl     CHO                                               376    Cyclo-C.sub.10 H.sub.19                                                                       Cl     CHO                                               377    CH.sub.2 CH.sub.2 Cl                                                                          Cl     CHO                                               378    CH.sub.2 CH.sub.2 OCH.sub.3                                                                   Cl     CHO                                               379    CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                            Cl     CHO                                               380    CH.sub.2 CH.sub.2 NH.sub.2                                                                    Cl     CHO                                               381    CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                           Cl     CHO                                               382    CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                    Cl     CHO                                               383    CH.sub.2 CH.sub.2 SCH.sub.3                                                                   Cl     CHO                                               384    CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                            Cl     CHO                                               385    (CH.sub.2).sub.3 Cl                                                                           Cl     CHO                                               386    (CH.sub.2).sub.3 OCH.sub.3                                                                    Cl     CHO                                               387    (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                             Cl     CHO                                               388    (CH.sub.2).sub.3 NH.sub.2                                                                     Cl     CHO                                               389    (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                            Cl     CHO                                               390    (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                     Cl     CHO                                               391    (CH.sub.2).sub.3 SCH.sub.3                                                                    Cl     CHO                                               392    (CH.sub.2).sub.3 SC.sub.2 H.sub.5                                                             Cl     CHO                                               393    CH.sub.2 C.sub.6 H.sub.5                                                                      Cl     CHO                                               394    CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                             Cl     CHO                                               395    CH(CH.sub.3)C.sub.6 H.sub.5                                                                   Cl     CHO                                               396    CH(C.sub.6 H.sub.5).sub.2                                                                     Cl     CHO                                               397    C.sub.6 H.sub.5                                                                               Cl     CHO   220-226                                     398    C.sub.6 H.sub.4 -(2)-Cl                                                                       Cl     CHO                                               399    C.sub.6 H.sub.4 -(3)-Cl                                                                       Cl     CHO                                               400    C.sub.6 H.sub.4 -(4)-Cl                                                                       Cl     CHO                                               401    C.sub.6 H.sub.4 -(2)-OCH.sub.3                                                                Cl     CHO                                               402    C.sub.6 H.sub.4 -(3)-OCH.sub.3                                                                Cl     CHO   123-130                                     403    C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                Cl     CHO   140-146                                     404    C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5                                                         Cl     CHO                                               405    C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5                                                         Cl     CHO                                               406    C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5                                                         Cl     CHO                                               407    C.sub.6 H.sub.4 -(2)-NO.sub.2                                                                 Cl     CHO                                               408    C.sub.6 H.sub.4 -(3)-NO.sub.2                                                                 Cl     CHO                                               409    C.sub. 6 H.sub.4 -(4)-NO.sub.2                                                                Cl     CHO                                               410    CH.sub.2COOCH.sub.3                                                                           Cl     CHO                                               411    CH.sub.2COOC.sub.2 H.sub.5                                                                    Cl     CHO                                               412    NH.sub.2       Cl     CHO                                               413    N(CH.sub.3).sub.2                                                                             Cl     CHO                                               414    N(C.sub.2 H.sub.5).sub.2                                                                      Cl     CHO                                               415    CH.sub.3       Br     CHO                                               416    C.sub.2 H.sub.5                                                                               Br     CHO                                               417    n-C.sub.3 H.sub.7                                                                             Br     CHO                                               418    iso-C.sub.3 H.sub.7                                                                           Br     CHO                                               419    n-C.sub.4 H.sub.9                                                                             Br     CHO                                               420    n-C.sub.13 H.sub.17                                                                           Br     CHO                                               421    Cyclo-C.sub.6 H.sub.11                                                                        Br     CHO                                               422    C.sub.6 H.sub.5                                                                               Br     CHO                                               423    C.sub.2 H.sub.4 Br                                                                            Br     CHO                                               424    NH.sub.2       Br     CHO                                               425    N(CH.sub.3).sub.2                                                                             Br     CHO                                               426    N(C.sub.2 H.sub.5).sub.2                                                                      Br     CHO                                               427    CH.sub.3       Cl     CH.sub.3                                          428    C.sub.2 H.sub.5                                                                               Cl     CH.sub.3                                          429    n-C.sub.3 H.sub.7                                                                             Cl     CH.sub.3                                          430    iso-C.sub.3 H.sub.7                                                                           Cl     CH.sub.3                                          431    n-C.sub.4 H.sub.9                                                                             Cl     CH.sub.3                                          432    n-C.sub.13 H.sub.17                                                                           Cl     CH.sub.3                                          433    Cyclo-C.sub.6 H.sub.11                                                                        Cl     CH.sub.3                                          434    C.sub.6 H.sub.5                                                                               Cl     CH.sub.3                                          435    C.sub.2 H.sub.4 Br                                                                            Cl     CH.sub.3                                          436    NH.sub. 2      Cl     CH.sub.3                                          437    N(CH.sub.3).sub.2                                                                             Cl     CH.sub.3                                          438    N(C.sub.2 H.sub.5).sub.2                                                                      Cl     CH.sub.3                                          439    CH.sub.3       Br     CH.sub.3                                          440    C.sub.2 H.sub.5                                                                               Br     CH.sub.3                                          441    n-C.sub.3 H.sub.7                                                                             Br     CH.sub.3                                          442    iso-C.sub.3 H.sub.7                                                                           Br     CH.sub.3                                          443    n-C.sub.4 H.sub.9                                                                             Br     CH.sub.3                                          444    n-C.sub.13 H.sub.17                                                                           Br     CH.sub.3                                          445    Cyclo-C.sub.6 H.sub.11                                                                        Br     CH.sub.3                                          446    C.sub.6 H.sub.5                                                                               Br     CH.sub.3                                          447    C.sub.2 H.sub.4 Br                                                                            Br     CH.sub.3                                          448    NH.sub.2       Br     CH.sub.3                                          449    N(CH.sub.3).sub.2                                                                             Br     CH.sub.3                                          450    N(C.sub.2 H.sub.5).sub.2                                                                      Br     CH.sub.3                                          451    CH.sub.3       Cl     C.sub.6 H.sub.5                                   452    C.sub.2 H.sub.5                                                                               Cl     C.sub.6 H.sub.5                                   453    n-C.sub.3 H.sub.7                                                                             Cl     C.sub.6 H.sub.5                                   454    iso-C.sub.3 H.sub.7                                                                           Cl     C.sub.6 H.sub.5                                   455    n-C.sub.4 H.sub.9                                                                             Cl     C.sub.6 H.sub.5                                   456    n-C.sub.13 H.sub.17                                                                           Cl     C.sub.6 H.sub.5                                   457    Cyclo-C.sub.6 H.sub.11                                                                        Cl     C.sub.6 H.sub.5                                   458    C.sub.6 H.sub.5                                                                               Cl     C.sub.6 H.sub.5                                   459    C.sub.2 H.sub.4 Br                                                                            Cl     C.sub.6 H.sub.5                                   460    NH.sub.2       Cl     C.sub.6 H.sub.5                                   461    N(CH.sub.3).sub.2                                                                             Cl     C.sub.6 H.sub.5                                   462    N(C.sub.2 H.sub.5).sub.2                                                                      Cl     C.sub.6 H.sub.5                                   463    CH.sub.3       Br     C.sub.6 H.sub.5                                   464    C.sub.2 H.sub.5                                                                               Br     C.sub.6 H.sub.5                                   465    n-C.sub.3 H.sub.7                                                                             Br     C.sub.6 H.sub.5                                   466    iso-C.sub.3 H.sub.7                                                                           Br     C.sub.6 H.sub.5                                   467    n-C.sub.4 H.sub.9                                                                             Br     C.sub.6 H.sub.5                                   468    n-C.sub.13 H.sub.17                                                                           Br     C.sub.6 H.sub.5                                   469    Cyclo-C.sub.6 H.sub.11                                                                        Br     C.sub.6 H.sub.5                                   470    C.sub.6 H.sub.5                                                                               Br     C.sub.6 H.sub.5                                   471    C.sub.2 H.sub.4 Br                                                                            Br     C.sub.6 H.sub.5                                   472    NH.sub.2       Br     C.sub.6 H.sub.5                                   473    N(CH.sub.3).sub.2                                                                             Br     C.sub.6 H.sub.5                                   474    N(C.sub.2 H.sub.5).sub.2                                                                      Br     C.sub.6 H.sub.5                                   475    CH.sub.3       Cl     H                                                 476    C.sub.2 H.sub.5                                                                               Cl     H                                                 477    n-C.sub.3 H.sub.7                                                                             Cl     H                                                 478    iso-C.sub.3 H.sub.7                                                                           Cl     H                                                 479    n-C.sub.4 H.sub.9                                                                             Cl     H                                                 480    n-C.sub.13 H.sub.17                                                                           Cl     H                                                 481    Cyclo-C.sub.6 H.sub.11                                                                        Cl     H                                                 482    C.sub.6 H.sub.5                                                                               Cl     H                                                 483    C.sub.2 H.sub.4 Br                                                                            Cl     H                                                 484    NH.sub.2       Cl     H                                                 485    N(CH.sub.3).sub.2                                                                             Cl     H                                                 486    N(C.sub.2 H.sub.5).sub.2                                                                      Cl     H                                                 487    CH.sub.3       Br     H                                                 488    C.sub.2 H.sub.5                                                                               Br     H                                                 489    n-C.sub.3 H.sub.7                                                                             Br     H                                                 490    iso-C.sub.3 H.sub.7                                                                           Br     H                                                 491    n-C.sub.4 H.sub.9                                                                             Br     H                                                 492    n-C.sub.13 H.sub.17                                                                           Br     H                                                 493    Cyclo-C.sub.6 H.sub.11                                                                        Br     H                                                 494    C.sub.6 H.sub.5                                                                               Br     H                                                 495    C.sub.2 H.sub.4 Br                                                                            Br     H                                                 496    NH.sub.2       Br     H                                                 497    N(CH.sub.3).sub.2                                                                             Br     H                                                 498    N(C.sub.2 H.sub.5).sub.2                                                                      Br     H                                                 ______________________________________                                    

EXAMPLE 499 2-Amino-4-chloro-5-formyl-1-methylpyrrole-3-carboxamide

9.54 g of 4-chloro-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole (Example 143) were refluxed in 100 ml of 5% by weight aqueous sodium hydroxide solution for one hour. After cooling, the precipitate was filtered off with suction, washed and dried. 4.00 g (50% of theory) of the compound of the formula ##STR48## of melting point 217° C. (decomposition) were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are constituent with the structural formula.

The compounds listed in Table 5 are obtained in a similar manner to Example 499.

                  TABLE 5                                                          ______________________________________                                          ##STR49##                                                                     Example                            Melting point                               No.     L.sup.1       L.sup.2                                                                               L.sup.3                                                                              [°C.]                                ______________________________________                                         500     C.sub.2 H.sub.5                                                                              Cl     CHO                                               501     n-C.sub.3 H.sub.7                                                                            Cl     CHO                                               502     iso-C.sub.3 H.sub.7                                                                          Cl     CHO                                               503     n-C.sub.4 H.sub.9                                                                            Cl     CHO                                               504     iso-C.sub.4 H.sub.9                                                                          Cl     CHO                                               505     sec-C.sub.4 H.sub.9                                                                          Cl     CHO                                               506     n-C.sub.5 H.sub.11                                                                           Cl     CHO                                               507     Neo-C.sub.5 H.sub.11                                                                         Cl     CHO                                               508     n-C.sub.6 H.sub.13                                                                           Cl     CHO                                               509     n-C.sub.7 H.sub.15                                                                           Cl     CHO                                               510     n-C.sub.8 H.sub.17                                                                           Cl     CHO                                               511     n-C.sub.9 H.sub.19                                                                           Cl     CHO                                               512     n-C.sub.10 H.sub.21                                                                          Cl     CHO                                               513     n-C.sub.11 H.sub.23                                                                          Cl     CHO                                               514     n-C.sub.12 H.sub.25                                                                          Cl     CHO                                               515     n-C.sub.13 H.sub.27                                                                          Cl     CHO                                               516     n-C.sub.14 H.sub.29                                                                          Cl     CHO                                               517     n-C.sub.15 H.sub.31                                                                          Cl     CHO                                               518     n-C.sub.16 H.sub.33                                                                          Cl     CHO                                               519     n-C.sub.17 H.sub. 35                                                                         Cl     CHO                                               520     n-C.sub.18 H.sub.37                                                                          Cl     CHO                                               521     n-C.sub.19 H.sub.39                                                                          Cl     CHO                                               522     n-C.sub.20 H.sub.41                                                                          Cl     CHO                                               523     Cyclo-C.sub.3 H.sub.5                                                                        Cl     CHO                                               524     Cyclo-C.sub.4 H.sub.7                                                                        Cl     CHO                                               525     Cyclo-C.sub.5 H.sub.9                                                                        Cl     CHO                                               526     Cyclo-C.sub.6 H.sub.11                                                                       Cl     CHO                                               527     Cyclo-C.sub.7 H.sub.13                                                                       Cl     CHO                                               528     Cyclo-C.sub.8 H.sub.15                                                                       Cl     CHO                                               529     Cyclo-C.sub.9 H.sub.17                                                                       Cl     CHO                                               530     Cyclo-C.sub.10 H.sub.19                                                                      Cl     CHO                                               531     CH.sub.2 CH.sub.2 Cl                                                                         Cl     CHO                                               532     CH.sub.2 CH.sub.2 OCH.sub.3                                                                  Cl     CHO                                               533     CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           Cl     CHO                                               534     CH.sub.2 CH.sub.2 NH.sub.2                                                                   Cl     CHO                                               535     CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                          Cl     CHO                                               536     CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                   Cl     CHO                                               537     CH.sub.2 CH.sub.2 SCH.sub.3                                                                  Cl     CHO                                               538     CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                           Cl     CHO                                               539     (CH.sub.2).sub.3 Cl                                                                          Cl     CHO                                               540     (CH.sub.2).sub.3 OCH.sub.3                                                                   Cl     CHO                                               541     (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                            Cl     CHO                                               542     (CH.sub.2).sub.3 NH.sub.2                                                                    Cl     CHO                                               543     (CH.sub. 2).sub.3 N(CH.sub.3).sub.2                                                          Cl     CHO                                               544     (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                    Cl     CHO                                               545     (CH.sub.2).sub.3 SCH.sub.3                                                                   Cl     CHO                                               546     (CH.sub.2).sub.3 SC.sub.2 H.sub.5                                                            Cl     CHO                                               547     CH.sub.2 C.sub.6 H.sub.5                                                                     Cl     CHO                                               548     CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                            Cl     CHO                                               549     CH(CH.sub.3)C.sub.6 H.sub.5                                                                  Cl     CHO                                               550     CH(C.sub.6 H.sub.5).sub.2                                                                    Cl     CHO                                               551     C.sub.6 H.sub.5                                                                              Cl     CHO                                               552     C.sub.6 H.sub.4 -(2)-Cl                                                                      Cl     CHO                                               553     C.sub.6 H.sub.4 -(3)-Cl                                                                      Cl     CHO                                               554     C.sub.6 H.sub.4 -(4)-Cl                                                                      Cl     CHO                                               555     C.sub.6 H.sub.4 -(2)-OCH.sub.3                                                               Cl     CHO                                               556     C.sub.6 H.sub.4 -(3)-OCH.sub.3                                                               Cl     CHO                                               557     C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                               Cl     CHO                                               558     C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5                                                        Cl     CHO                                               559     C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5                                                        Cl     CHO                                               560     C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5                                                        Cl     CHO                                               561     C.sub.6 H.sub.4 -(2)-NO.sub.2                                                                Cl     CHO                                               562     C.sub.6 H.sub.4 -(3)-NO.sub.2                                                                Cl     CHO                                               563     C.sub.6 H.sub.4 -(4)-NO.sub.2                                                                Cl     CHO                                               564     CH.sub. 2COOCH.sub.3                                                                         Cl     CHO                                               565     CH.sub.2COOC.sub.2 H.sub.5                                                                   Cl     CHO                                               566     NH.sub.2      Cl     CHO                                               567     N(CH.sub.3).sub.2                                                                            Cl     CHO                                               568     N(C.sub.2 H.sub.5).sub.2                                                                     Cl     CHO                                               569     CH.sub.3      Br     CHO                                               570     C.sub.2 H.sub.5                                                                              Br     CHO                                               571     n-C.sub.3 H.sub.7                                                                            Br     CHO                                               572     iso-C.sub.3 H.sub.7                                                                          Br     CHO                                               573     n-C.sub.4 H.sub.9                                                                            Br     CHO                                               574     n-C.sub.13 H.sub.17                                                                          Br     CHO                                               575     Cyclo-C.sub.6 H.sub.11                                                                       Br     CHO                                               576     C.sub.6 H.sub.5                                                                              Br     CHO                                               577     C.sub.2 H.sub.4 Br                                                                           Br     CHO                                               578     NH.sub.2      Br     CHO                                               579     N(CH.sub.3).sub.2                                                                            Br     CHO                                               580     N(C.sub.2 H.sub.5).sub.2                                                                     Br     CHO                                               581     CH.sub.3      Cl     CH.sub.3                                          582     C.sub.2 H.sub.5                                                                              Cl     CH.sub.3                                          583     n-C.sub.3 H.sub.7                                                                            Cl     CH.sub.3                                          584     iso-C.sub.3 H.sub.7                                                                          Cl     CH.sub.3                                          585     n-C.sub.4 H.sub.9                                                                            Cl     CH.sub.3                                          586     n-C.sub.13 H.sub.17                                                                          Cl     CH.sub.3                                          587     Cyclo-C.sub.6 H.sub.11                                                                       Cl     CH.sub.3                                          588     C.sub.6 H.sub.5                                                                              Cl     CH.sub.3                                          589     C.sub.2 H.sub.4 Cl                                                                           Cl     CH.sub.3                                          590     NH.sub.2      Cl     CH.sub.3                                          591     N(CH.sub.3).sub.2                                                                            Cl     CH.sub.3                                          592     N(C.sub.2 H.sub.5).sub.2                                                                     Cl     CH.sub.3                                          593     CH.sub.3      Br     CH.sub.3                                          594     C.sub.2 H.sub.5                                                                              Br     CH.sub.3                                          595     n-C.sub.3 H.sub.7                                                                            Br     CH.sub.3                                          596     iso-C.sub.3 H.sub.7                                                                          Br     CH.sub.3                                          597     n-C.sub.4 H.sub.9                                                                            Br     CH.sub.3                                          598     n-C.sub.13 H.sub.17                                                                          Br     CH.sub.3                                          599     Cyclo-C.sub.6 H.sub.11                                                                       Br     CH.sub.3                                          600     C.sub.6 H.sub.5                                                                              Br     CH.sub.3                                          601     C.sub.2 H.sub.4 Br                                                                           Br     CH.sub.3                                          602     NH.sub.2      Br     CH.sub.3                                          603     N(CH.sub.3).sub.2                                                                            Br     CH.sub.3                                          604     N(C.sub.2 H.sub.5).sub.2                                                                     Br     CH.sub.3                                          605     CH.sub.3      Cl     C.sub.6 H.sub.5                                   606     C.sub.2 H.sub.5                                                                              Cl     C.sub.6 H.sub.5                                   607     n-C.sub.3 H.sub.7                                                                            Cl     C.sub.6 H.sub.5                                   608     iso-C.sub.3 H.sub.7                                                                          Cl     C.sub.6 H.sub.5                                   609     n-C.sub.4 H.sub.9                                                                            Cl     C.sub.6 H.sub.5                                   610     n-C.sub.13 H.sub.17                                                                          Cl     C.sub.6 H.sub.5                                   611     Cyclo-C.sub.6 H.sub.11                                                                       Cl     C.sub.6 H.sub.5                                   612     C.sub.6 H.sub.5                                                                              Cl     C.sub.6 H.sub.5                                   613     C.sub.2 H.sub.4 Cl                                                                           Cl     C.sub.6 H.sub.5                                   614     NH.sub.2      Cl     C.sub.6 H.sub.5                                   615     N(CH.sub.3).sub.2                                                                            Cl     C.sub.6 H.sub.5                                   616     N(C.sub.2 H.sub.5).sub.2                                                                     Cl     C.sub.6 H.sub.5                                   617     CH.sub.3      Br     C.sub.6 H.sub.5                                   618     C.sub.2 H.sub.5                                                                              Br     C.sub.6 H.sub.5                                   619     n-C.sub.3 H.sub.7                                                                            Br     C.sub.6 H.sub.5                                   620     iso-C.sub.3 H.sub.7                                                                          Br     C.sub.6 H.sub.5                                   621     n-C.sub.4 H.sub.9                                                                            Br     C.sub.6 H.sub.5                                   622     n-C.sub.13 H.sub.17                                                                          Br     C.sub.6 H.sub.5                                   623     Cyclo-C.sub.6 H.sub.11                                                                       Br     C.sub.6 H.sub.5                                   624     C.sub.6 H.sub.5                                                                              Br     C.sub.6 H.sub.5                                   625     C.sub.2 H.sub.4 Br                                                                           Br     C.sub.6 H.sub.5                                   626     NH.sub.2      Br     C.sub.6 H.sub.5                                   627     N(CH.sub.3).sub.2                                                                            Br     C.sub.6 H.sub.5                                   628     N(C.sub.2 H.sub.5).sub.2                                                                     Br     C.sub.6 H.sub.5                                   629     CH.sub.3      Cl     H                                                 630     C.sub.2 H.sub.5                                                                              Cl     H                                                 631     n-C.sub.3 H.sub.7                                                                            Cl     H                                                 632     iso-C.sub.3 H.sub.7                                                                          Cl     H                                                 633     n-C.sub.4 H.sub.9                                                                            Cl     H                                                 634     n-C.sub.13 H.sub.17                                                                          Cl     H                                                 635     Cyclo-C.sub.6 H.sub.11                                                                       Cl     H                                                 636     C.sub.6 H.sub.5                                                                              Cl     H                                                 637     C.sub.2 H.sub.4 OH                                                                           Cl     H                                                 638     NH.sub.2      Cl     H                                                 639     N(CH.sub.3).sub.2                                                                            Cl     H                                                 640     N(C.sub.2 H.sub.5).sub.2                                                                     Cl     H                                                 641     CH.sub.3      Br     H                                                 642     C.sub.2 H.sub.5                                                                              Br     H                                                 643     n-C.sub.3 H.sub.7                                                                            Br     H                                                 644     iso-C.sub.3 H.sub.7                                                                          Br     H                                                 645     n-C.sub.4 H.sub.9                                                                            Br     H                                                 646     n-C.sub.13 H.sub.17                                                                          Br     H                                                 647     Cyclo-C.sub.6 H.sub.11                                                                       Br     H                                                 648     C.sub.6 H.sub.5                                                                              Br     H                                                 649     C.sub.2 H.sub.4 Br                                                                           Br     H                                                 650     NH.sub.2      Br     H                                                 651     N(CH.sub.3).sub.2                                                                            Br     H                                                 652     N(C.sub.2 H.sub.5).sub.2                                                                     Br     H                                                 ______________________________________                                    

EXAMPLE 653 4-Chloro-3-cyano-2-dimethylformamidino-1-methylpyrrole-5-carbaldehyde oxime

7.2 g of 4-chloro-3-cyano-2-dimethylformamidino-5formyl-1-methylpyrrole (Example 143), 4.2 g of hydroxylammonium chloride and 5.1 g of sodium bicarbonate were refluxed in 100 ml of ethanol/water (1:1) for 3 hours. After cooling, 0.5 l of water was added, and the precipitate was filtered off with suction, washed and dried. 5.5 g of the compound of the formula ##STR50## of melting point 220° to 220° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

The compounds listed in Table 6 are obtained in a similar manner to Example 653.

                  TABLE 6                                                          ______________________________________                                          ##STR51##                                                                     Example                           Melting point                                No.     L.sup.1            L.sup.2                                                                               [°C.]                                 ______________________________________                                         654     C.sub.2 H.sub.5    Cl                                                  655     n-C.sub.3 H.sub.7  Cl                                                  656     iso-C.sub.3 H.sub.7                                                                               Cl                                                  657     n-C.sub.4 H.sub.9  Cl                                                  658     iso-C.sub.4 H.sub.9                                                                               Cl                                                  659     sec-C.sub.4 H.sub.9                                                                               Cl                                                  660     n-C.sub.5 H.sub.11 Cl                                                  661     Neo-C.sub.5 H.sub.11                                                                              Cl                                                  662     n-C.sub.6 H.sub.13 Cl                                                  663     n-C.sub.7 H.sub.15 Cl                                                  664     n-C.sub.8 H.sub.17 Cl                                                  665     n-C.sub.9 H.sub.19 Cl                                                  666     n-C.sub.10 H.sub.21                                                                               Cl                                                  667     n-C.sub.11 H.sub.23                                                                               Cl                                                  668     n-C.sub.12 H.sub.25                                                                               Cl                                                  669     n-C.sub.13 H.sub.27                                                                               Cl                                                  670     n-C.sub.14 H.sub.29                                                                               Cl                                                  671     n-C.sub.15 H.sub.31                                                                               Cl                                                  672     n-C.sub.16 H.sub.33                                                                               Cl                                                  673     n-C.sub.17 H.sub.35                                                                               Cl                                                  674     n-C.sub.18 H.sub.37                                                                               Cl                                                  675     n-C.sub.19 H.sub.39                                                                               Cl                                                  676     n-C.sub.20 H.sub. 41                                                                              Cl                                                  677     Cyclo-C.sub.3 H.sub.5                                                                             Cl                                                  678     Cyclo-C.sub.4 H.sub.7                                                                             Cl                                                  679     Cyclo-C.sub.5 H.sub.9                                                                             Cl                                                  680     Cyclo-C.sub.6 H.sub.11                                                                            Cl                                                  681     Cyclo-C.sub.7 H.sub.13                                                                            Cl                                                  682     Cyclo-C.sub.8 H.sub.15                                                                            Cl                                                  683     Cyclo-C.sub.9 H.sub.17                                                                            Cl                                                  684     Cyclo-C.sub.10 H.sub.19                                                                           Cl                                                  685     CH.sub.2 CH.sub.2 Cl                                                                              Cl                                                  686     CH.sub.2 CH.sub.2 OCH.sub.3                                                                       Cl                                                  687     CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                                Cl                                                  688     CH.sub.2 CH.sub.2 NCHN(CH.sub.3).sub.2                                                            Cl                                                  689     CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                               Cl                                                  690     CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        Cl                                                  691     CH.sub.2 CH.sub.2 SCH.sub.3                                                                       Cl                                                  692     CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                                Cl                                                  693     (CH.sub.2).sub.3 Cl                                                                               Cl                                                  694     (CH.sub.2).sub.3 OCH.sub.3                                                                        Cl                                                  695     (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                                 Cl                                                  696     (CH.sub.2).sub.3 NCHN(CH.sub.3).sub.2                                                             Cl                                                  697     (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                                Cl                                                  698     (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                         Cl                                                  699     (CH.sub.2).sub.3 SCH.sub.3                                                                        Cl                                                  700     (CH.sub.2).sub.3 SC.sub. 2 H.sub.5                                                                Cl                                                  701     CH.sub.2 C.sub.6 H.sub.5                                                                          Cl                                                  702     CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                                 Cl                                                  703     CH(CH.sub.3)C.sub.6 H.sub.5                                                                       Cl                                                  704     CH(C.sub.6 H.sub.5).sub.2                                                                         Cl                                                  705     C.sub.6 H.sub.5    Cl                                                  706     C.sub.6 H.sub.4 -(2)-Cl                                                                           Cl                                                  707     C.sub.6 H.sub.4 -(3)-Cl                                                                           Cl                                                  708     C.sub.6 H.sub.4 -(4)-Cl                                                                           Cl                                                  709     C.sub.6 H.sub.4 -(2)-OCH.sub.3                                                                    Cl                                                  710     C.sub.6 H.sub.4 -(3)-OCH.sub.3                                                                    Cl                                                  711     C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                    Cl                                                  712     C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5                                                             Cl                                                  713     C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5                                                             Cl                                                  714     C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5                                                             Cl                                                  715     C.sub.6 H.sub.4 -(2)-NO.sub.2                                                                     Cl                                                  716     C.sub.6 H.sub.4 -(3)-NO.sub.2                                                                     Cl                                                  717     C.sub.6 H.sub.4 -(4)-NO.sub.2                                                                     Cl                                                  718     CH.sub.2COOCH.sub.3                                                                               Cl                                                  719     CH.sub.2COOC.sub.2 H.sub.5                                                                        Cl                                                  720     NCHN(CH.sub.3).sub.2                                                                              Cl                                                  721     N(CH.sub.3).sub.2  Cl                                                  722     N(C.sub.2 H.sub.5).sub.2                                                                          Cl                                                  723     CH.sub.3           Br                                                  724     C.sub.2 H.sub.5    Br                                                  725     n-C.sub.3 H.sub.7  Br                                                  726     iso-C.sub.3 H.sub.7                                                                               Br                                                  727     CH.sub.2 CH.sub.2 NH.sub.2                                                                        Br                                                  728     CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                               Br                                                  729     Cyclo-C.sub.6 H.sub.11                                                                            Br                                                  730     C.sub.6 H.sub.5    Br                                                  731     C.sub.2 H.sub.4 Br Br                                                  732     NH.sub.2           Br                                                  733     N(CH.sub.3).sub.2  Br                                                  734     N(C.sub.2 H.sub.5).sub.2                                                                          Br                                                  ______________________________________                                    

EXAMPLE 735 2-Acetylamino-4-chloro-3,5-dicyano-1-metylpyrrole

5.0 g of 4-chloro-b 3-cyano-2-dimethylformamidino-1-metylpyrrole-5-carbaldehyde oxime (Example 653) were refluxed in 40 ml of acetic anhydride for 15 hours. After addition of 100 ml of water the reaction mixture was refluxed for a further 10 minutes and then poured into 300 g of ice. The mixture was adjusted to pH 5 with 50% concentrated sodium hydroxide solution, and the precipitate was left to stand at room temperature for two hours and then filtered off with suction, washed and dried. 2.2 g (47% of theory) of the compound of the formula ##STR52## of melting point 180° to 182° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

The compounds listed in Table 7 are obtained in a similar manner to Example 735.

                  TABLE 7                                                          ______________________________________                                          ##STR53##                                                                     Example                           Melting point                                No.     L.sup.1           L.sup.2 [°C.]                                 ______________________________________                                         736     C.sub.2 H.sub.5   Cl                                                   737     n-C.sub.3 H.sub.7 Cl                                                   738     iso-C.sub.3 H.sub.7                                                                              Cl                                                   739     n-C.sub.4 H.sub.9 Cl                                                   740     iso-C.sub.4 H.sub.9                                                                              Cl                                                   741     sec-C.sub.4 H.sub.9                                                                              Cl                                                   742     n-C.sub.5 H.sub.11                                                                               Cl                                                   743     Neo-C.sub.5 H.sub.11                                                                             Cl                                                   744     n-C.sub.6 H.sub.13                                                                               Cl                                                   745     n-C.sub.7 H.sub.15                                                                               Cl                                                   746     n-C.sub.8 H.sub.17                                                                               Cl                                                   747     n-C.sub.9 H.sub.19                                                                               Cl                                                   748     n-C.sub.10 H.sub.21                                                                              Cl                                                   749     n-C.sub.11 H.sub.23                                                                              Cl                                                   750     n-C.sub.12 H.sub.25                                                                              Cl                                                   751     n-C.sub.13 H.sub.27                                                                              Cl                                                   752     n-C.sub.14 H.sub.29                                                                              Cl                                                   753     n-C.sub.15 H.sub.31                                                                              Cl                                                   754     n-C.sub.16 H.sub.33                                                                              Cl                                                   755     n-C.sub.17 H.sub.35                                                                              Cl                                                   756     n-C.sub.18 H.sub.37                                                                              Cl                                                   757     n-C.sub.19 H.sub.39                                                                              Cl                                                   758     n-C.sub.20 H.sub.41                                                                              Cl                                                   759     Cyclo-C.sub.3 H.sub.5                                                                            Cl                                                   760     Cyclo-C.sub.4 H.sub.7                                                                            Cl                                                   761     Cyclo-C.sub.5 H.sub.9                                                                            Cl                                                   762     Cyclo-C.sub.6 H.sub.11                                                                           Cl                                                   763     Cyclo-C.sub.7 H.sub.13                                                                           Cl                                                   764     Cyclo-C.sub.8 H.sub.15                                                                           Cl                                                   765     Cyclo-C.sub.9 H.sub.17                                                                           Cl                                                   766     Cyclo-C.sub.10 H.sub.19                                                                          Cl                                                   767     CH.sub.2 CH.sub.2 Cl                                                                             Cl                                                   768     CH.sub.2 CH.sub.2 OCH.sub.3                                                                      Cl                                                   769     CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                               Cl                                                   770     CH.sub.2 CH.sub.2 NCHN(CH.sub.3).sub.2                                                           Cl                                                   771     CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                              Cl                                                   772     CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       Cl                                                   773     CH.sub.2 CH.sub.2 SCH.sub.3                                                                      Cl                                                   774     CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                               Cl                                                   775     (CH.sub.2).sub.3 Cl                                                                              Cl                                                   776     (CH.sub.2).sub.3 OCH.sub.3                                                                       Cl                                                   777     (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                                Cl                                                   778     (CH.sub.2).sub.3 NCHN(CH.sub.3).sub.2                                                            Cl                                                   779     (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                               Cl                                                   780     (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                        Cl                                                   781     (CH.sub.2).sub.3 SCH.sub.3                                                                       Cl                                                   782     (CH.sub.2).sub.3 SC.sub.2 H.sub.5                                                                Cl                                                   783     CH.sub.2 C.sub.6 H.sub.5                                                                         Cl                                                   784     CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                                Cl                                                   785     CH(CH.sub.3)C.sub.6 H.sub.5                                                                      Cl                                                   786     CH(C.sub.6 H.sub.5).sub.2                                                                        Cl                                                   787     C.sub.6 H.sub.5   Cl                                                   788     C.sub.6 H.sub.4 -(2)-Cl                                                                          Cl                                                   789     C.sub.6 H.sub.4 -(3)-Cl                                                                          Cl                                                   790     C.sub.6 H.sub.4 -(4)-Cl                                                                          Cl                                                   791     C.sub.6 H.sub.4 -(2)-OCH.sub.3                                                                   Cl                                                   792     C.sub.6 H.sub.4 -(3)-OCH.sub.3                                                                   Cl                                                   793     C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                   Cl                                                   794     C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5                                                            Cl                                                   795     C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5                                                            Cl                                                   796     C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5                                                            Cl                                                   797     C.sub.6 H.sub.4 -(2)-NO.sub.2                                                                    Cl                                                   798     C.sub.6 H.sub.4 -(3)-NO.sub.2                                                                    Cl                                                   799     C.sub.6 H.sub.4 -(4)-NO.sub.2                                                                    Cl                                                   800     CH.sub.2COOCH.sub.3                                                                              Cl                                                   801     CH.sub.2COOC.sub.2 H.sub.5                                                                       Cl                                                   802     NCHN(CH.sub.3).sub.2                                                                             Cl                                                   803     N(CH.sub.3).sub.2 Cl                                                   804     N(C.sub.2 H.sub.5).sub.2                                                                         Cl                                                   805     CH.sub.3          Br                                                   806     C.sub.2 H.sub.5   Br                                                   807     n-C.sub.3 H.sub.7 Br                                                   808     iso-C.sub.3 H.sub.7                                                                              Br                                                   809     n-C.sub.4 H.sub.9 Br                                                   810     n-C.sub.13 H.sub.17                                                                              Br                                                   811     Cyclo-C.sub.6 H.sub.11                                                                           Br                                                   812     C.sub.6 H.sub.5   Br                                                   813     C.sub.2 H.sub.4 Br                                                                               Br                                                   814     N(CH.sub.3).sub.2 Br                                                   815     N(C.sub.2 H.sub.5).sub.2                                                                         Br                                                   ______________________________________                                    

EXAMPLE 816 4-chloro-3,5-dicyano-2-dimethylformamidino-1-methylpyrrole

4.8 g of 4-chloro-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole (Example 143) and 1.8 g of copper(I) cyanide in 50 ml of DMF were refluxed for 5 days. The reaction mixture was cooled and then filtered, and 200 ml of water were added to the filtrate. The precipitate was filtered off with suction, washed and dried. 1.4 g (30% of theory) of the compound of the formula ##STR54## of melting point 180° to 184° C. were obtained The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

The compounds listed in Table 8 are obtained in a similar manner to Example 816.

                  TABLE 8                                                          ______________________________________                                          ##STR55##                                                                     Example                        Melting point                                   No.        L.sup.1       L.sup.2                                                                              [°C.]                                    ______________________________________                                         816        CH.sub.3      Cl                                                    817        C.sub.2 H.sub.5                                                                              Cl                                                    818        n-C.sub.3 H.sub.7                                                                            Cl                                                    819        iso-C.sub.3 H.sub.7                                                                          Cl                                                    820        n-C.sub.4 H.sub.9                                                                            Cl                                                    821        iso-C.sub.4 H.sub.9                                                                          Cl                                                    822        sec-C.sub.4 H.sub.9                                                                          Cl                                                    823        n-C.sub.5 H.sub.11                                                                           Cl                                                    824        Neo-C.sub.5 H.sub.11                                                                         Cl                                                    825        n-C.sub.6 H.sub.13                                                                           Cl                                                    826        n-C.sub.7 H.sub.15                                                                           Cl                                                    827        n-C.sub.8 H.sub.17                                                                           Cl                                                    828        n-C.sub.9 H.sub.19                                                                           Cl                                                    829        n-C.sub.10 H.sub.21                                                                          Cl                                                    830        n-C.sub.11 H.sub.23                                                                          Cl                                                    831        n-C.sub.12 H.sub.25                                                                          Cl                                                    832        n-C.sub.13 H.sub.27                                                                          Cl                                                    833        n-C.sub.14 H.sub.29                                                                          Cl                                                    834        n-C.sub.15 H.sub.31                                                                          Cl                                                    835        n-C.sub.16 H.sub.33                                                                          Cl                                                    836        n-C.sub.17 H.sub.35                                                                          Cl                                                    837        n-C.sub.18 H.sub.37                                                                          Cl                                                    838        n-C.sub.19 H.sub.39                                                                          Cl                                                    839        n-C.sub.20 H.sub.41                                                                          Cl                                                    840        Cyclo-C.sub.3 H.sub.5                                                                        Cl                                                    841        Cyclo-C.sub.4 H.sub.7                                                                        Cl                                                    842        Cyclo-C.sub.5 H.sub.9                                                                        Cl                                                    843        Cyclo-C.sub.6 H.sub.11                                                                       Cl                                                    844        Cyclo-C.sub.7 H.sub.13                                                                       Cl                                                    845        Cyclo-C.sub.8 H.sub.15                                                                       Cl                                                    846        Cyclo-C.sub.9 H.sub.17                                                                       Cl                                                    847        Cyclo-C.sub.10 H.sub.19                                                                      Cl                                                    848        CH.sub.2C.sub.6 H.sub.5                                                                      Cl                                                    849        CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                            Cl                                                    850        CH(CH.sub.3).sub.2 C.sub.6 H.sub.5                                                           Cl                                                    851        CH(C.sub.6 H.sub.5).sub.2                                                                    Cl                                                    852        C.sub.6 H.sub.5                                                                              Cl                                                    ______________________________________                                    

EXAMPLE 853 5-Acetyl-2-acetylamino-4-acetyloxy-3-cyano-1-methylpyrrole

4.11 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1) and 4.92 g of sodium acetate were refluxed in 50 ml of acetic anhydride for one hour. 150 ml of water were added and the mixture was then boiled for a further 30 minutes and then cooled to room temperature. The precipitate was filtered off with suction, washed and dried. 6.7 g (85% of theory) of the compound of the formula ##STR56## of melting point 140° to 141° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

The compounds listed in Table 9 are obtained in a similar manner to Example 853

                                      TABLE 9                                      __________________________________________________________________________      ##STR57##                                                                     Example                            Melting point                               No.  L.sup.1         L.sup.2 L.sup.3                                                                              [°C.]                                __________________________________________________________________________     853  CH.sub.3        COCH.sub.3                                                                             CH.sub.3                                          854  C.sub.2 H.sub.5 COCH.sub.3                                                                             CH.sub.3                                          855  n-C.sub.3 H.sub.7                                                                              COCH.sub.3                                                                             CH.sub.3                                          856  iso-C.sub.3 H.sub.7                                                                            COCH.sub.3                                                                             CH.sub.3                                          857  n-C.sub.4 H.sub.9                                                                              COCH.sub.3                                                                             CH.sub.3                                          858  iso-C.sub.4 H.sub.9                                                                            COCH.sub.3                                                                             CH.sub.3                                          859  sec-C.sub.4 H.sub.9                                                                            COCH.sub.3                                                                             CH.sub.3                                          860  n-C.sub.5 H.sub.11                                                                             COCH.sub.3                                                                             CH.sub.3                                          861  Neo-C.sub.5 H.sub.11                                                                           COCH.sub.3                                                                             CH.sub.3                                          862  n-C.sub.6 H.sub.13                                                                             COCH.sub.3                                                                             CH.sub.3                                          863  n-C.sub.7 H.sub.15                                                                             COCH.sub.3                                                                             CH.sub.3                                          864  n-C.sub.8 H.sub.17                                                                             COCH.sub.3                                                                             CH.sub.3                                          865  n-C.sub.9 H.sub.19                                                                             COCH.sub.3                                                                             CH.sub.3                                          866  n-C.sub.10 H.sub.21                                                                            COCH.sub.3                                                                             CH.sub.3                                          867  n-C.sub.11 H.sub. 23                                                                           COCH.sub.3                                                                             CH.sub.3                                          868  n-C.sub.12 H.sub.25                                                                            COCH.sub.3                                                                             CH.sub.3                                          869  n-C.sub.13 H.sub.27                                                                            COCH.sub.3                                                                             CH.sub.3                                          870  n-C.sub.14 H.sub.29                                                                            COCH.sub.3                                                                             CH.sub.3                                          871  n-C.sub.15 H.sub.31                                                                            COCH.sub.3                                                                             CH.sub.3                                          872  n-C.sub.16 H.sub.33                                                                            COCH.sub.3                                                                             CH.sub.3                                          873  n-C.sub.17 H.sub.35                                                                            COCH.sub.3                                                                             CH.sub.3                                          874  n-C.sub.18 H.sub.37                                                                            COCH.sub.3                                                                             CH.sub.3                                          875  n-C.sub.19 H.sub.39                                                                            COCH.sub.3                                                                             CH.sub.3                                          876  n-C.sub.20 H.sub.41                                                                            COCH.sub.3                                                                             CH.sub.3                                          877  CH.sub.2 CHCH.sub.2                                                                            COCH.sub.3                                                                             CH.sub.3                                          878  CH.sub.2 OCH    COCH.sub.3                                                                             CH.sub.3                                          879  Cyclo-C.sub.3 H.sub.5                                                                          COCH.sub.3                                                                             CH.sub.3                                          880  Cyclo-C.sub.4 H.sub.7                                                                          COCH.sub.3                                                                             CH.sub.3                                          881  Cyclo-C.sub.6 H.sub.11                                                                         COCH.sub.3                                                                             CH.sub.3                                          882  Cyclo-C.sub.7 H.sub.13                                                                         COCH.sub.3                                                                             CH.sub.3                                          883  Cyclo-C.sub.8 H.sub.15                                                                         COCH.sub.3                                                                             CH.sub.3                                          884  Cyclo-C.sub.9 H.sub.17                                                                         COCH.sub.3                                                                             CH.sub.3                                          885  Cyclo-C.sub.10 H.sub.19                                                                        COCH.sub.3                                                                             CH.sub.3                                          886  CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  COCH.sub.3                                                                             CH.sub.3                                          887  CH.sub.2 CH.sub.2 OCH.sub.3                                                                    COCH.sub.3                                                                             CH.sub.3                                          888  CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                             COCH.sub.3                                                                             CH.sub.3                                          889  CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                                 COCH.sub.3                                                                             CH.sub.3                                          890  CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                            COCH.sub.3                                                                             CH.sub.3                                          891  CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                     COCH.sub.3                                                                             CH.sub.3                                          892  CH.sub.2 CH.sub.2 SCH.sub.3                                                                    COCH.sub.3                                                                             CH.sub.3                                          893  CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                             COCH.sub.3                                                                             CH.sub.3                                          894  (CH.sub.2).sub.3 OCOCH.sub.3                                                                   COCH.sub.3                                                                             CH.sub.3                                          895  (CH.sub.2).sub.3 OCH.sub.3                                                                     COCH.sub.3                                                                             CH.sub.3                                          896  (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                              COCH.sub.3                                                                             CH.sub.3                                          897  (CH.sub.2).sub.3 NHCOCH.sub.3                                                                  COCH.sub.3                                                                             CH.sub.3                                          898  (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                             COCH.sub.3                                                                             CH.sub.3                                          899  (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                      COCH.sub.3                                                                             CH.sub.3                                          900  (CH.sub.2).sub.3 SCH.sub.3                                                                     COCH.sub.3                                                                             CH.sub.3                                          901  (CH.sub.2).sub.3 SC.sub.2 H.sub.5                                                              COCH.sub.3                                                                             CH.sub.3                                          902  CH.sub.2 C.sub.6 H.sub.5                                                                       COCH.sub.3                                                                             CH.sub.3                                          903  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              COCH.sub.3                                                                             CH.sub.3                                          904  CH(CH.sub.3 )C.sub.6 H.sub.5                                                                   COCH.sub.3                                                                             CH.sub.3                                          905  CH(C.sub.6 H.sub.5).sub.2                                                                      COCH.sub.3                                                                             CH.sub.3                                          906  C.sub.6 H.sub.5 COCH.sub.3                                                                             CH.sub.3                                          907  C.sub.6 H.sub.4 -(2)-Cl                                                                        COCH.sub.3                                                                             CH.sub.3                                          908  C.sub.6 H.sub.4 -(3)-Cl                                                                        COCH.sub.3                                                                             CH.sub.3                                          909  C.sub.6 H.sub.4 -(4)-Cl                                                                        COCH.sub.3                                                                             CH.sub.3                                          910  C.sub.6 H.sub.4 -(2)-NO.sub.2                                                                  COCH.sub.3                                                                             CH.sub.3                                          911  C.sub.6 H.sub.4 -(3)-NO.sub.2                                                                  COCH.sub.3                                                                             CH.sub.3                                          912  C.sub.6 H.sub.4 -(4)-NO.sub.2                                                                  COCH.sub.3                                                                             CH.sub.3                                          913  C.sub.6 H.sub.4 -(2)-CN                                                                        COCH.sub.3                                                                             CH.sub.3                                          914  C.sub.6 H.sub.4 -(3)-CN                                                                        COCH.sub.3                                                                             CH.sub.3                                          915  C.sub.6 H.sub.4 -(4)-CN                                                                        COCH.sub.3                                                                             CH.sub.3                                          916  C.sub.6 H.sub.4 -(2)-COOCH.sub.3                                                               COCH.sub.3                                                                             CH.sub.3                                          917  C.sub.6 H.sub.4 -(3)-COOCH.sub.3                                                               COCH.sub.3                                                                             CH.sub.3                                          918  C.sub.6 H.sub.4 -(4)-COOCH.sub.3                                                               COCH.sub.3                                                                             CH.sub.3                                          919  Pyrid-2-yl      COCH.sub.3                                                                             CH.sub.3                                          920  Pyrid-3-yl      COCH.sub.3                                                                             CH.sub.3                                          921  Pyrid-4-yl      COCH.sub.3                                                                             CH.sub.3                                          922  CH.sub.2COOCH.sub.3                                                                            COCH.sub.3                                                                             CH.sub.3                                          923  CH.sub.2COOC.sub.2 H.sub.5                                                                     COCH.sub.3                                                                             CH.sub.3                                          924  NHCOCH.sub.3    COCH.sub.3                                                                             CH.sub.3                                          925  N(CH.sub.3).sub.2                                                                              COCH.sub.3                                                                             CH.sub.3                                          926  N(C.sub.2 H.sub.5).sub.2                                                                       COCH.sub.3                                                                             CH.sub.3                                          927  CH.sub.3        CH.sub.3                                                                               CH.sub.3                                          928  C.sub.2 H.sub.5 CH.sub.3                                                                               CH.sub.3                                          929  iso-C.sub.3 H.sub.7                                                                            CH.sub.3                                                                               CH.sub.3                                          930  CH.sub.2 CHCH.sub.2                                                                            CH.sub.3                                                                               CH.sub.3                                          931  Cyclo-C.sub.6 H.sub.11                                                                         CH.sub.3                                                                               CH.sub.3                                          932  CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  CH.sub.3                                                                               CH.sub.3                                          933  CH.sub.2 CH.sub.2 OCH.sub.3                                                                    CH.sub.3                                                                               CH.sub.3                                          934  C.sub.6 H.sub.5 CH.sub.3                                                                               CH.sub.3                                          935  Pyrid-3-yl      CH.sub.3                                                                               CH.sub.3                                          936  NHCOCH.sub.3    CH.sub.3                                                                               CH.sub.3                                          937  CH.sub.3        C.sub.6 H.sub.5                                                                        CH.sub.3                                          938  C.sub.2 H.sub.5 C.sub.6 H.sub.5                                                                        CH.sub.3                                          939  iso-C.sub.3 H.sub.7                                                                            C.sub.6 H.sub.5                                                                        CH.sub.3                                          940  CH.sub.2 CHCH.sub.2                                                                            C.sub.6 H.sub.5                                                                        CH.sub.3                                          941  CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  C.sub.6 H.sub.5                                                                        CH.sub.3                                          942  CH.sub.2 CH.sub.2 OCH.sub.3                                                                    C.sub.6 H.sub.5                                                                        CH.sub.3                                          943  C.sub.6 H.sub.5 C.sub.6 H.sub.5                                                                        CH.sub.3                                          944  C.sub.6 H.sub.4 -(4)-CN                                                                        C.sub.6 H.sub.5                                                                        CH.sub.3                                          945  NHCOCH.sub.3    C.sub.6 H.sub.5                                                                        CH.sub.3                                          946  (CH.sub.2).sub.3OCH.sub.2 C.sub.6 H.sub.5                                                      COCH.sub.3                                                                             CH.sub.3                                          947  (CH.sub.2).sub.3O(CH.sub.2).sub.2OC.sub.6 H.sub.5                                              COCH.sub.3                                                                             CH.sub.3                                          948  CH.sub.3        COCH(CH.sub.3).sub.2                                                                   CH(CH.sub.3).sub.2                                949  CH.sub.3        COC.sub.6 H.sub.5                                                                      C.sub.6 H.sub.5                                   950  CH.sub.3        CO-n-C.sub.6 H.sub.13                                                                  n-C.sub.6 H.sub.13                                __________________________________________________________________________

EXAMPLE 951

4.1 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1), 4.2 g of hydroxylammonium chloride and 5.1 g of sodium bicarbonate are refluxed in 100 ml of H₂ O/ethanol (1:1) for 3 hours. The mixture was cooled to room temperature and then diluted with H₂ O, and the precipitate was filtered off with suction. 4.2 g (83% of theory) of the compound of the formula ##STR58## of melting point >260° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

The compounds listed in the following Table 10 are obtained in a similar manner

                                      TABLE 10                                     __________________________________________________________________________      ##STR59##                                                                     Example                           Melting point                                No.  L.sup.1         L.sup.2   L.sup.3                                                                           [°C.]                                 __________________________________________________________________________     952  C.sub.2 H.sub.5 NH.sub.2  H                                               953  n-C.sub.3 H.sub.7                                                                              NH.sub.2  H                                               954  iso-C.sub.3 H.sub.7                                                                            NH.sub.2  H                                               955  n-C.sub.4 H.sub.9                                                                              NH.sub.2  H                                               956  iso-C.sub.4 H.sub.9                                                                            NH.sub.2  H                                               957  sec-C.sub.4 H.sub.9                                                                            NH.sub.2  H                                               958  n-C.sub.5 H.sub.11                                                                             NH.sub.2  H                                               959  Neo-C.sub.5 H.sub.11                                                                           NH.sub.2  H                                               960  n-C.sub.6 H.sub.13                                                                             NH.sub.2  H                                               961  n-C.sub.7 H.sub.15                                                                             NH.sub.2  H                                               962  n-C.sub.8 H.sub.17                                                                             NH.sub.2  H                                               963  n-C.sub.9 H.sub.19                                                                             NH.sub.2  H                                               964  n-C.sub.10 H.sub.21                                                                            NH.sub.2  H                                               965  n-C.sub.11 H.sub.23                                                                            NH.sub.2  H                                               966  n-C.sub.12 H.sub.25                                                                            NH.sub.2  H                                               967  n-C.sub.13 H.sub.27                                                                            NH.sub.2  H                                               968  n-C.sub.14 H.sub. 29                                                                           NH.sub.2  H                                               969  n-C.sub.15 H.sub.31                                                                            NH.sub.2  H                                               970  n-C.sub.16 H.sub.33                                                                            NH.sub.2  H                                               971  n-C.sub.17 H.sub.35                                                                            NH.sub.2  H                                               972  n-C.sub.18 H.sub.37                                                                            NH.sub.2  H                                               973  n-C.sub.19 H.sub.39                                                                            NH.sub.2  H                                               974  n-C.sub.20 H.sub.41                                                                            NH.sub.2  H                                               975  CH.sub.2 CHCH.sub.2                                                                            NH.sub.2  H                                               976  CH.sub.2 CCH    NH.sub.2  H                                               977  Cyclo-C.sub.3 H.sub.5                                                                          NH.sub.2  H                                               978  Cyclo-C.sub.4 H.sub.7                                                                          NH.sub.2  H                                               979  Cyclo-C.sub.5 H.sub.9                                                                          NH.sub.2  H                                               980  Cyclo-C.sub.6 H.sub.11                                                                         NH.sub.2  H                                               981  Cyclo-C.sub.7 H.sub.13                                                                         NH.sub.2  H                                               982  Cyclo-C.sub.8 H.sub.15                                                                         NH.sub.2  H                                               983  Cyclo-C.sub.9 H.sub.17                                                                         NH.sub.2  H                                               984  Cyclo-C.sub.10 H.sub.19                                                                        NH.sub.2  H                                               985  CH.sub.2 CH.sub.2 OH                                                                           NH.sub.2  H                                               986  CH.sub.2 CH.sub.2 OCH.sub.3                                                                    NH.sub.2  H                                               987  CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                             NH.sub.2  H                                               988  CH.sub.2 CH.sub.2 NH.sub.2                                                                     NH.sub.2  H                                               989  CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                            NH.sub.2  H                                               990  CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                     NH.sub.2  H                                               991  CH.sub.2 CH.sub.2 SCH.sub.3                                                                    NH.sub.2  H                                               992  CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                             NH.sub.2  H                                               993  (CH.sub.2).sub.3 OH                                                                            NH.sub.2  H                                               994  (CH.sub.2).sub.3 OCH.sub.3                                                                     NH.sub.2  H                                               995  (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                              NH.sub.2  H                                               996  (CH.sub.2).sub.3 NH.sub.2                                                                      NH.sub.2  H                                               997  (CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                             NH.sub.2  H                                               998  (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                      NH.sub.2  H                                               999  (CH.sub.2).sub.3 SCH.sub.3                                                                     NH.sub.2  H                                               1000 (CH.sub.2).sub.3 SC.sub.2 H.sub.5                                                              NH.sub.2  H                                               1001 CH.sub.2 C.sub.6 H.sub.5                                                                       NH.sub.2  H  205 (dec)                                    1002 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  H  190 (dec)                                    1003 CH(CH.sub.3)C.sub.6 H.sub.5                                                                    NH.sub.2  H                                               1004 CH(C.sub.6 H.sub.5).sub.2                                                                      NH.sub.2  H                                               1005 C.sub.6 H.sub.5 NH.sub.2  H  210 (dec)                                    1006 C.sub.6 H.sub.4 -(2)-OH                                                                        NH.sub.2  H                                               1007 C.sub.6 H.sub.4 -(3)-OH                                                                        NH.sub.2  H                                               1008 C.sub.6 H.sub.4 -(4)-OH                                                                        NH.sub.2  H                                               1009 C.sub.6 H.sub.4 -(2)-OCH.sub.3                                                                 NH.sub.2  H                                               1010 C.sub.6 H.sub.4 -(3)-OCH.sub.3                                                                 NH.sub.2  H  240 (dec)                                    1011 C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                 NH.sub.2  H  220 (dec)                                    1012 C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5                                                          NH.sub.2  H                                               1013 C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5                                                          NH.sub.2  H                                               1014 C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5                                                          NH.sub.2  H                                               1015 C.sub.6 H.sub.4 -(2)-Cl                                                                        NH.sub.2  H                                               1016 C.sub.6 H.sub.4 -(3)-Cl                                                                        NH.sub.2  H                                               1017 C.sub.6 H.sub.4 -(4)-Cl                                                                        NH.sub.2  H                                               1018 C.sub.6 H.sub.4 -(2)-NO.sub.2                                                                  NH.sub.2  H                                               1019 C.sub.6 H.sub.4 -(3)-NO.sub.2                                                                  NH.sub.2  H                                               1020 C.sub.6 H.sub.4 -(4)-NO.sub.2                                                                  NH.sub.2  H                                               1021 C.sub.6 H.sub.4 -(2)-NH.sub.2                                                                  NH.sub.2  H                                               1022 C.sub.6 H.sub.4 -(3)-NH.sub.2                                                                  NH.sub.2  H                                               1023 C.sub.6 H.sub.4 -(4)-NH.sub.2                                                                  NH.sub.2  H                                               1024 C.sub.6 H.sub.4 -(2)-CH.sub.3                                                                  NH.sub.2  H  190 (dec)                                    1025 C.sub.6 H.sub.4 -(3)-CH.sub.3                                                                  NH.sub.2  H                                               1026 C.sub.6 H.sub.4 -(4)-CH.sub.3                                                                  NH.sub.2  H                                               1027 C.sub.6 H.sub.4 -(2)-C.sub.2 H.sub. 5                                                          NH.sub.2  H                                               1028 C.sub.6 H.sub.4 -(3)-C.sub.2 H.sub.5                                                           NH.sub.2  H                                               1029 C.sub.6 H.sub.4 -(4)-C.sub.2 H.sub.5                                                           NH.sub.2  H                                               1030 C.sub.6 H.sub.4 -(2)-CN                                                                        NH.sub.2  H                                               1031 C.sub.6 H.sub.4 -(3)-CN                                                                        NH.sub.2  H                                               1032 C.sub.6 H.sub.4 -(4)-CN                                                                        NH.sub.2  H                                               1033 C.sub.6 H.sub.4 -(2)-COOCH.sub.3                                                               NH.sub.2  H                                               1034 C.sub.6 H.sub.4 -(3)-COOCH.sub.3                                                               NH.sub.2  H                                               1035 C.sub.6 H.sub.4 -(4)-COOCH.sub.3                                                               NH.sub.2  H                                               1036 Pyrid-2-yl      NH.sub.2  H                                               1037 Pyrid-3-yl      NH.sub.2  H                                               1038 Pyrid-4-yl      NH.sub.2  H                                               1039 (CH.sub.2).sub.2C.sub.6 H.sub.3 -(3)-Cl-(2)-CH.sub.3                                           NH.sub.2  H                                               1040 (CH.sub.2).sub.2C.sub.6 H.sub.4 -(3,4)-(OCH.sub.3).sub.2                                       NH.sub.2  H                                               1041 (CH.sub.2).sub.2C.sub.6 H.sub.3 -(2)-Cl                                                        NH.sub.2  H                                               1042 C.sub.6 H.sub.3 -(3,4)-Cl.sub.2                                                                NH.sub.2  H                                               1043 CH.sub.2COOCH.sub.3                                                                            NH.sub.2  H                                               1044 CH.sub.2COOC.sub.2 H.sub.5                                                                     NH.sub.2  H                                               1045 NH.sub.2        NH.sub.2  H                                               1046 N(CH.sub.3).sub.2                                                                              NH.sub.2  H                                               1047 N(C.sub.2 H.sub.5).sub.2                                                                       NH.sub.2  H                                               1048 H               N(CH.sub.3).sub. 2                                                                       H                                               1049 H               N(C.sub.2 H.sub.5).sub.2                                                                 H                                               1050 H               N(n-C.sub.3 H.sub.7).sub.2                                                               H                                               1051 H               N(n-C.sub.4 H.sub.9).sub.2                                                               H                                               1052 H                                                                                               ##STR60##                                                                               H                                               1053 H                                                                                               ##STR61##                                                                               H                                               1054 H                                                                                               ##STR62##                                                                               H                                               1055 H                                                                                               ##STR63##                                                                               H                                               1056 H                                                                                               ##STR64##                                                                               H                                               1057 H                                                                                               ##STR65##                                                                               H                                               1058 CH.sub.3        NH.sub.2  CH.sub.3                                        1059 C.sub.2 H.sub.5 NH.sub.2  CH.sub.3                                        1060 iso-C.sub.3 H.sub.7                                                                            NH.sub.2  CH.sub.3                                        1061 CH.sub.2 CHCH.sub.2                                                                            NH.sub.2  CH.sub.3                                        1062 Cyclo-C.sub.6 H.sub.11                                                                         NH.sub.2  CH.sub.3                                        1063 CH.sub.2 CH.sub.2 OH                                                                           NH.sub.2  CH.sub.3                                        1064 CH.sub.2 CH.sub.2 OCH.sub.3                                                                    NH.sub.2  CH.sub.3                                        1065 CH.sub.2 C.sub.6 H.sub.5                                                                       NH.sub.2  CH.sub.3                                        1066 C.sub.6 H.sub.5 NH.sub.2  CH.sub. 3                                       1067 C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                 NH.sub.2  CH.sub.3                                        1068 C.sub.6 H.sub.4 -(2)-CH.sub.3                                                                  NH.sub.2  CH.sub.3                                        1069 (3)-Pyridyl     NH.sub.2  CH.sub.3                                        1070 NH.sub.2        NH.sub.2  CH.sub.3                                        1071 H               N(CH.sub.3).sub.2                                                                        CH.sub.3                                        1072 H               N(C.sub.2 H.sub.5).sub.2                                                                 CH.sub.3                                        1073 H                                                                                               ##STR66##                                                                               CH.sub.3                                        1074 H                                                                                               ##STR67##                                                                               CH.sub.3                                        1075 CH.sub.3        NH.sub.2  C.sub.6 H.sub.5                                 1076 C.sub.2 H.sub.5 NH.sub.2  C.sub.6 H.sub.5                                 1077 iso-C.sub.3 H.sub.7                                                                            NH.sub.2  C.sub.6 H.sub.5                                 1078 CH.sub.2 CHCH.sub.2                                                                            NH.sub.2  C.sub.6 H.sub.5                                 1079 CH.sub.2 CH.sub.2 OH                                                                           NH.sub.2  C.sub.6 H.sub.5                                 1080 CH.sub.2 CH.sub.2 OCH.sub.3                                                                    NH.sub.2  C.sub.6 H.sub.5                                 1081 CH.sub.2 C.sub.6 H.sub.5                                                                       NH.sub.2  C.sub.6 H.sub.5                                 1082 C.sub.6 H.sub.5 NH.sub.2  C.sub.6 H.sub.5                                 1083 C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                 NH.sub.2  C.sub.6 H.sub.5                                 1084 C.sub.6 H.sub.4 -(4)-CN                                                                        NH.sub.2  C.sub.6 H.sub.5                                 1085 NH.sub.2        NH.sub.2  C.sub.6 H.sub.5                                 1086 H               N(CH.sub.3).sub.2                                                                        C.sub.6 H.sub.5                                 1087 H               N(C.sub.2 H.sub.5).sub.2                                                                 C.sub.6 H.sub.5                                 1088 H                                                                                               ##STR68##                                                                               C.sub.6 H.sub.5                                 1089 H                                                                                               ##STR69##                                                                               C.sub.6 H.sub.5                                 1090 (CH.sub.2).sub.3OCH.sub.2 C.sub.6 H.sub.5                                                      NH.sub.2  H                                               1091 (CH.sub.2).sub.3O(CH.sub.2).sub.2OC.sub.6 H.sub.5                                              NH.sub.2  H                                               __________________________________________________________________________

EXAMPLE 1092

10.0 g of 3-chloro-4-cyano-5-dimethylformamidino-2-formyl-1-methylpyrrole and 6.1 g of Meldrum's acid were stirred in 100 ml of dimethylformamide and 1 ml of piperidine at 50° C. for 15 hours. 200 ml of water were added and the precipitate was filtered off with suction and dried. 5.2 g (34% of theory) of the compound of the formula ##STR70## of melting point 199° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

EXAMPLE 1093

6.6 g of malononitrile were dissolved in 200 ml of n-propanol. To this were added 5 g of sodium acetate and 11.9 g of 4-chloro-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole and the mixture was stirred at room temperature for 8 hours. The precipitate was filtered off with suction, washed with n-propanol and dried. 13.2 g (92% of theory) of the compound of the formula ##STR71## of melting point 180° C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.

The compounds listed in the following Table 11 are obtained in a similar manner.

                                      TABLE 11                                     __________________________________________________________________________      ##STR72##                                                                     Example                            Melting point                               No.  L.sup.1                                                                               L.sup.2      L.sup.3   [°C.]                                __________________________________________________________________________     1094 CH.sub.3                                                                              CHC(COOCH.sub.3).sub.2                                                                      NCHN(CH.sub.3).sub.2                                                                     175                                         1095 C.sub.2 H.sub.5                                                                       CHC(COOCH.sub.3).sub.2                                                                      NCHN(CH.sub.3).sub.2                                  1096 C.sub.6 H.sub.5                                                                       CHC(COOC.sub.2 H.sub.5).sub.2                                                               NCHN(CH.sub.3).sub.2                                  1097 CH(CH.sub.3).sub.2                                                                    CHC(COOC.sub.2 H.sub.5).sub.2                                                               NH.sub.2                                              1098 C.sub.2 H.sub.5                                                                       CHC(CN).sub.2                                                                               NCHN(CH.sub.3).sub.2                                  1099 n-C.sub.4 H.sub.9                                                                     CHC(CN).sub.2                                                                               NCHN(CH.sub.3).sub.2                                  1100 CH.sub.3                                                                              CHC(COOCH.sub.3)(CN)                                                                        NCHN(CH.sub.3).sub.2                                  1101 C.sub.6 H.sub.5                                                                       CHC(COOC.sub.2 H.sub.5)(CN)                                                                 NH.sub.2                                              1102 C.sub.6 H.sub.5 CH.sub.2                                                              CHC(COOCH.sub.3)(CN)                                                                        NCHN(CH.sub.3).sub.2                                  1103 C.sub.6 H.sub.5                                                                       CHC(COOCH.sub.3)(CN)                                                                        NH.sub.2                                              1104 CH.sub.3                                                                               ##STR73##   NCHN(CH.sub.3).sub.2                                  1105 C.sub.2 H.sub.5                                                                        ##STR74##   NH.sub.2                                              1106 CH.sub.3                                                                              CHC(CONHCH.sub.3)(CN)                                                                       NCHN(CH.sub.3).sub.2                                  1107 C.sub.6 H.sub.5                                                                       CHC(COCH.sub.3)(CN)                                                                         NH.sub.2                                              1108 Cyclo-C.sub.6 H.sub.11                                                                CHC(COC.sub.6 H.sub.5)(CN)                                                                  NCHN(CH.sub.3).sub.2                                  1109 CH.sub.3                                                                              CHC(C.sub.6 H.sub.5)(CN)                                                                    NCHN(CH.sub.3).sub.2                                  1110 CH(CH.sub.3).sub.2                                                                     ##STR75##   NCHN(CH.sub.3).sub.2                                  1111 CH.sub.3                                                                               ##STR76##   NH.sub.2                                              1112 CH(CH.sub.3).sub.2                                                                     ##STR77##   NH.sub.2                                              1113 CH.sub.3                                                                              CHCHNO.sub.2 NCHN(CH.sub.3).sub.2                                  1114 CH(CH.sub.3).sub.2                                                                    CHC(CH.sub.3)NO.sub.2                                                                       NCHN(CH.sub.3).sub.2                                  __________________________________________________________________________ 

We claim:
 1. A pyrrole derivative of the formula I ##STR78## or the tautomer thereof, where R¹ is hydrogen, C₁ -C₂₀ -alkyl which can be substituted with C₁ -C₅ -alkylthio, phenoxy, halogen, hydroxyl, amino, C₁ -C₄ mono- or dialkylamino, pyrrolidino, C₁ -C₅ -alkoxycarbonyl, or phenyl which can be substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro, hydroxyl, or amino; C₁ -C₂₀ -alkyl which can be substituted with C₁ -C₅ -alkylthio, phenoxy, halogen, hydroxyl, amino, C₁ -C₄ mono- or dialkylamino, pyrrolidino, C₁ -C₅ -alkoxycarbonyl, or phenyl which can be substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro, hydroxyl, or amino and interrupted by one or more oxygen; C₃ -C₆ -alkenyl which can be substituted with fluorine, chlorine, or bromine; C₃ -C₆ -alkynyl which can be substituted with fluorine, chlorine, or bromine; C₃ -C₁₀ -cycloalkyl which can be substituted with fluorine, chlorine, or bromine; phenyl which can be substituted with C₁ -C₄ -alkyl, C₁ 14 C₄ -alkoxy, halogen, nitro, hydroxyl, or amino; thienyl, amino, C₁ C₄ -alkanoylamino, benzoylamino, C₁ C₄ -dialkylamino or ##STR79## where X¹ is C₁ -C₄ -alkyl or phenyl, and X² is C₁ 14 C₄ -alkyl, is hydrogen, C₁ -C₄ -alkyl, benzyl, C₃ -C₆ -alkenyl, C₅ -C₇ -cycloalkyl, or phenyl which can be substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro, hydroxyl, or amino;R³ is hydrogen, C₁ -C₄ -alkyl, benzyl or C₃ -C₆ -alkenyl, or R² and R³ together are ##STR80## where T¹ is hydrogen, C₁ -C₄ -alkyl or phenyl, T² is C₁ -C₄ -alkyl, or phenyl which can be substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro, hydroxyl, or amino; and T³ is C₁ C₄ -alkyl, or R² and R³ together with the nitrogen connecting them is pyrrolidino, R⁴ is cyano, carbamoyl, C₁ -C₄ -mono- or dialkylcarbamoyl, thiocarbamoyl, C₁ -C₄ -mono- or dialkylthiocarbamoyl or ##STR81## R⁵ is halogen, hydroxyl, C₁ -C₂₀ -alkanoyloxy, or benzoyloxy and R⁶ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro, hydroxyl, or amino; cyano, halogen, nitro, hydroxysulfonyl, C₁ -C₁₀ -alkanoyl, benzoyl, or ##STR82## where T⁴ is C₁ -C₄ -alkyl, or phenyl which can be substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro, hydroxyl, or amino; and T⁵ is the radical of an active methylene compound, hydroxylimino or N--X³ where X³ is C₁ -C₂₀ -alkyl which can be substituted with C₁ -C₅ -alkylthio, phenoxy, halogen, hydroxyl, amino, C₁ -C₄ mono-or dialkylamino, pyrrolidino, C₁ -C₅ -alkoxycarbonyl, or phenyl which can be substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro, hydroxyl, or amino; C₁ -C₂₀ -alkyl which can be substituted with C₁ -C₅ -alkylthio, phenoxy, halogen, hydroxyl, amino, C₁ -C₄ mono- or dialkylamino, pyrrolidino, C₁ -C₅ -alkoxycarbonyl, or phenyl which can be substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro, hydroxyl, or amino and interrupted by one or more oxygen; C₃ -C₆ -alkenyl which can be substituted with fluorine, chlorine, or bromine; C₃ -C₆ -alkynyl which can be substituted with fluorine, chlorine, or bromine; C₃ -C₁₀ -cycloalkyl which can be substituted with fluorine, chlorine, or bromine; phenyl which can be substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro, hydroxyl, or amino; C₁ -C₄ -alkoxycarbonylmethyl, amino, C₁ C₄ -dialkylamino or phenylamino, with the proviso that R¹, R² and R³ are not all hydrogen.
 2. A pyrrole derivative as claimed in claim 1, whereinR¹ is hydrogen, C₁ -C₁₅ -alkyl, C₅ -C₇ -cycloalkyl, C₃ -C₅ -alkenyl, C₂ -C₅ -hydroxyalkyl, C₂ C₅ -halogenoalkyl, C₁ -C₅ -alkoxy-C₂ -C₅ -alkyl, phenoxy-C₂ -C₅ -alkoxy-C₂ -C₅ -alkyl, phenyl-C₁ -C₅ -alkoxy-C₂ -C₅ -alkoxy-C₂ -C₅ -alkyl, C₁ -C₅ -alkylthio-C₂ -C₅ -alkyl, C₁ -C₅ -dialkylamino-C₂ -C₅ -alkyl, phenyl-C₁ -C₅ -alkyl, C₁ -C₅ -alkoxycarbonyl-C₁ -C₅ -alkyl, --(CH₂)_(n) --Y where n is from 1 to 5 and Y is pyrrolidino, phenyl, amino or C₁ -C₅ -dialkylamino, R² is hydrogen, C₁ -C₄ -alkyl, allyl, benzyl or phenyl, R³ is hydrogen, C₁ -C₄ -alkyl, allyl or benzyl or R² R³ together are ##STR83## where T¹ is hydrogen, C₁ -C₄ -alkyl, T² is C₁ -C₄ -alkyl or phenyl, and T³ is C₁ C₄ -alkyl, or R² and R³ together with the nitrogen connecting them is pyrrolidino, R⁴ is cyano, carbamoyl, thiocarbamoyl, or ##STR84## R⁵ is fluorine, chlorine, bromine, hydroxyl, C₁ -C₆ -alkanoyloxy or benzoyloxy and R⁶ is hydrogen, C₁ -C₄ -alkyl, phenyl, C₁ -C₆ -alkanoyl, benzoyl, cyano, chlorine, bromine, nitro, hydroxysulfonyl or ##STR85## where T⁴ and T⁵ each have the meaning indicated in claim
 1. 3. A pyrrole derivative as claimed in claim 1, whereinR¹ is hydrogen, C₁ -C₁₀ -alkyl, C₃ -C₄ -alkenyl, benzyl, phenyl or amino, R² is hydrogen, C₁ -C₄ -alkyl, allyl, benzyl or phenyl, R³ is hydrogen, C₁ -C₄ -alkyl or allyl, or R² and R³ together with the nitrogen connecting them is pyrrolidino, R⁴ is cyano, carbamoyl, thiocarbamoyl or ##STR86## R⁵ is chlorine, bromine, hydroxyl, C₁ -C₆ -alkanoyloxy or benzoyloxy and R⁶ is hydrogen, C₁ -C₄ -alkyl, phenyl, C₁ -C₆ -alkanoyl, benzoyl, cyano or ##STR87## where Z¹ and Z² are identical or different and, independently of one another, are each cyano, C₁ -C₄ -alkoxycarbonyl or nitro, and X³ has the meaning mentioned in claim
 1. 4. A pyrrole compound as claimed in claim 1, whereinR¹ is C₁ -C₄ -alkyl, phenyl or amino and R² and R³ are each hydrogen or R¹ is hydrogen, R² is methyl, ethyl, allyl, benzyl or phenyl, R³ is methyl, ethyl or allyl or R² and R³ together with the nitrogen connecting them is pyrrolidino, R⁴ is cyano or carbamoyl, R⁵ is chlorine, bromine or hydroxyl, R⁶ is hydrogen, formyl, cyano or ##STR88## where Z¹ and Z² are identical or different and, independently of one another, are each cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl or nitro. 